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Journal of Environmental Management 226 (2018) 386–399
Contents lists available at ScienceDirect
Journal of Environmental Management
journal homepage: www.elsevier.com/locate/jenvman
Research article
Assessment of the use of organic composts derived from municipal solid
waste for the adsorption of Pb, Zn and Cd
T
Jacqueline Z. Limaa, Isabela M. Raimondia, Valdir Schalchb, Valéria G.S. Rodriguesa,∗
a
b
Department of Geotechnical Engineering, São Carlos School of Engineering, University of São Paulo, 400 Trabalhador Sãocarlense Ave, São Carlos, Brazil
Department of Hydraulics and Sanitary Engineering, São Carlos School of Engineering, University of São Paulo, 400 Trabalhador Sãocarlense Ave, São Carlos, Brazil
A R T I C LE I N FO
A B S T R A C T
Keywords:
Organic fraction of municipal solid waste
Composting
Physical and chemical characterization
Potentially toxic elements
Batch equilibrium test
Sorption
Waste management is a continuous global need. To minimize problems arising from municipal solid waste
(MSW) disposal, composting has emerged as a simple alternative for the organic fraction of the waste. The
composting process generates organic composts with a high metal retention capacity for potentially toxic elements (PTE). Thus, our objective was to examine how different composting methods (windrow composting, wire
mesh composting bin, and passively aerated static pile composting) affect the final product, and how the
characteristics of the generated composts influence their adsorption capacity for the lead (Pb), zinc (Zn) and
cadmium (Cd) elements from mining waste. Therefore, the physical and chemical properties of Brazilian composts were investigated, as well as their adsorption capacities, through batch equilibrium tests with Pb, Zn and
Cd in single-element solutions. All composts revealed promising adsorption characteristics, including a nearneutral pH (6.4–7.7); a negative ΔpH (−0.4 to −1.0); oxidizing conditions (Eh between +267.67
and + 347.00 mV); a considerable presence of organic matter (193.92–418.70 g kg−1); a substantial (albeit very
varied) cation exchange capacity (29.00–75.00 cmolc kg−1); and significant porosity (pore volume between
0.01113 and 0.05400 cm3 g−1). These results showed that the composts share similar intrinsic characteristics,
indicating that the different composting methods influenced subtly the physical and chemical properties of the
final products. Overall, the removal selectivity follows the order Pb > Cd > Zn, with the removal percentage
ranging from 94.0 to 99.6% for Pb, 55.4–89.8% for Cd and 22.1–64.0% for Zn. Thus, the joint assessment of the
characterization and adsorption results shows evidence that composts, a low-cost organic material produced
from waste, may be promising as alternative reactive materials for remediation of soils contaminated by Pb, Zn
and Cd.
1. Introduction
Waste, water and energy management are key issues for municipal
administrations. In fact, globally, MSW is a growing cause for concern
as the human population continues to expand, increasing consumption
levels and the subsequent need for waste disposal (Leal Filho et al.,
2016). Global MSW generation amounts to almost 1.3 billion tonnes per
year, with an expected increase to approximately 2.2 billion tonnes per
year by 2025. This represents an increase in the global waste generation
rate per capita from 1.20 to 1.42 kg per person per day in the coming
years. However, it is important to note that these are global averages
and that rates vary considerably depending on the region, country, city,
and even within cities (Hoornweg and Bhada-Tata, 2012).
Regarding the composition of MSW, the typology of the wastes and
their respective percentages of occurrence are affected by factors such
as culture, economic development, climate, and energy sources. At the
global level, the organic fraction constitutes the largest portion of solid
waste (46%), followed by paper (17%), plastic (10%), glass (5%), metal
(4%), and other wastes (18%). Considering the economic factor, the
MSW composition in developing countries consists mostly of organic
waste, whereas in developed countries, the largest proportion consists
of paper, plastic and other inorganic materials.
In Brazil, 51.4% of the originated and collected MSW corresponds to
the organic fraction (IPEA, 2012). Considering Brazilian legislation,
especially the National Solid Waste Policy (PNRS), established by Law
12,305 on August 2nd, 2010 and regulated by Decree 7404 on December 23, 2010 (Brasil, 2010a; 2010b), it is necessary to promote
environmentally friendly solid waste management by municipalities.
∗
Corresponding author. Department of Geotechnical Engineering, São Carlos School of Engineering, University of São Paulo, 400 Trabalhador Sãocarlense Ave.,
São Carlos, 13566-590, Brazil.
E-mail address: valguima@usp.br (V.G.S. Rodrigues).
https://doi.org/10.1016/j.jenvman.2018.08.047
Received 11 April 2018; Received in revised form 13 July 2018; Accepted 9 August 2018
0301-4797/ © 2018 Elsevier Ltd. All rights reserved.
Journal of Environmental Management 226 (2018) 386–399
J.Z. Lima et al.
concentrations of Zn and Cd). This amendment decreased mobile PTE
contents, with the restoration of soil chemistry and microbiota. This
possibility represents the combined management of two different types
of solid waste: organic municipal solid waste, used as the input for
compost generation, and mining waste, containing considerable concentrations of metals that should be immobilized by organic composts.
This combined management has not been widely studied, justifying the
present research.
Therefore, the objectives of this study are (1) to characterize
Brazilian organic composts originating from different composting
methods (physical, chemical, physicochemical, morphological and
elemental experimental analysis), as the standards regulating the
characterization of composts are usually limited to agricultural activity,
making it sometimes necessary to adjust existing regulations for soils
and peats (organic materials); (2) to evaluate the potential of using
these composts as low-cost reactive materials in metal cation immobilization, through batch equilibrium tests (with Pb, Zn and Cd); and
(3) to jointly assess the characterization and adsorption results to
support decision-making when evaluating the potential applicability of
said composts for the remediation of PTE-contaminated regions (in this
case, Pb, Zn and Cd), aimed at stability and equilibrium in the shortand long-term.
The simplicity and the rapid and easy implementation of composting technologies may provide a highly viable management alternative for the organic fraction of MSW, especially when considering the
characteristics and limitations of developing countries such as Brazil.
Moreover, considering a life cycle inventory assessment in which waste
disposal is a key component, composting can be regarded as a biological
treatment requiring less economic resources compared to other options
that would demand higher implementation and maintenance costs
(Thanh and Matsui, 2012; Jara-Samaniego et al., 2017).
Therefore, what was originally used as a simple, small-scale process
through so-called “yard composting” has received renewed interest
over the past two decades and is now seen as a way to address present
challenges in waste management. In particular, composting can serve as
an alternative for decreasing the amount of organic matter sent to
landfills, with a subsequent reduction in greenhouse gas emissions
(Saveyn and Eder, 2014; Cerda et al., 2017; Jara-Samaniego et al.,
2017) and increase in the service life of landfills.
From a systematic perspective, the effectiveness of composting depends on management of many factors, such as temperature, oxygen
(aeration), moisture content, pH, the C/N ratio and porosity (FAO,
2003; EPA, 2016; Cerda et al., 2017; Onwosi et al., 2017). To this end,
several technologies and composting systems have been deployed
(Kumar, 2011; EPA, 2016). This includes traditional methods, such as
windrow - the most commonly used aerobic digestion technique for the
biodegradable fraction (De Bertoldi et al., 1982; Ishii and Takii, 2003;
Vigneswaran et al., 2016; De Silva and Yatawara, 2017) and static piles
– with or without passive aeration (Vigneswaran et al., 2016), up to the
modern in-vessel composting reactors (Wang et al., 2016; Waqas et al.,
2018). To optimize the composting of household organic waste, there
should be an assessment of other systems, such as a wire mesh composting bin (Karnchanawong and Suriyanon, 2011; Karnchanawong
and Nissaikla, 2014).
In recent years, research has been conducted and new technologies
have been developed to obtain highly pure composts (Saveyn and Eder,
2014) with guaranteed maturity (Li et al., 2015), higher nutrient and
lower PTE contents (Saha et al., 2010; Huerta-Pujol et al., 2011;
Hoornweg and Bhada-Tata, 2012; Sharifi and Renella, 2015). Studies
have shown the possibility of optimizing of composting using biochar
(Vandecasteele et al., 2016; Waqas et al., 2018), microbial inoculation
(Karnchanawong and Nissaikla, 2014; Onwosi et al., 2017) and that
earthworm activity can effectively destroy bacterial pathogens in vermicomposting (Soobhany, 2018).
The main use of compost is as an organic fertilizer, favouring the
growth and development of plants; this is a way of adding value to this
material and can also be regarded as an environmentally friendly solution by minimizing the need for chemical applications (Lelis and
Pereira Neto, 1999; Kiehl, 2004; Mehta et al., 2014). Data from the
Brazilian Association of Fertilizer Diffusion (ANDA) shows that Brazil –
a worldwide agribusiness power – imported over 70% of the fertilizers
sold nationally in 2016. Hence, although using organic fertilizers does
not quench the demand for mineral fertilizers in a conventional agriculture context, composting may be an option for reduction and diversification. Indirectly, the increase in the amounts of compost added
to the soil possibly increased its pH, which can be agriculturally interesting because acidic soils are predominant in most of Brazil (Jordão
et al., 2006).
Nonetheless, beyond the classic agricultural use, organic composts
may also be regarded as reactive materials with a high PTE adsorption
potential, stemming from the large presence of humic substances
(Farrell et al., 2010; Zhou et al., 2017), favouring its use in the treatment of industrial wastewater (Kocasoy and Güvener, 2009) and in the
remediation of metal-contaminated soils (Farrell et al., 2010; Farrell
and Jones, 2010a; Paradelo and Barral, 2012; Venegas et al., 2015;
Simantiraki and Gidarakos, 2015; Zhou et al., 2017). Abad-Valle et al.
(2017) indicated that the compost derived from MSW was the most
efficient remediator of polluted mine soil (containing high
2. Materials and methods
2.1. Sample preparation
The organic composts used herein were synthesized at mid-scale
and under environmental conditions from the organic fraction of the
solid waste from the campus restaurant of the São Carlos School of
Engineering, University of São Paulo (Brazil), via different composting
methods: windrow composting, wire mesh composting bin, and passively aerated static pile composting. These methods were adapted to
the study scale.
Windrow composting is a procedure based on overlaying organic
fraction layers in a quadrangular format over branches, leaves, sawdust,
or even matured compost, placed at the base of the compost pile. The
organic residues are deposited in the centre, and dry matter is placed on
the lateral and upper surfaces.
Wire mesh composting bin involves filling a vertical cylindrical wire
mesh structure using, once again, twigs (in this case, pineapple crowns)
as the base to avoid direct contact with the soil. In this pile, the organic
residue must be deposited on the inside of the wire mesh structure, and
the inner side must be covered with straw, preventing the contact of
waste with the exterior. The vertical setup allows for better aeration, as
air circulates with greater ease through the compost mass.
Passively aerated static pile composting is based on an overlay
system, with the organic residue being placed at the base, directly over
the soil. Each layer of residue must be covered with dry matter, and a
new waste mass is added on top of the previous layer of straw and must
be covered with a new straw layer.
The composting process occurred between the last week of March
and the second week of June 2016. The effect of the composting system
on the final product was assessed via three heaps – one per composting
method – containing pre-preparation organic waste from the campus
restaurant (peels, stalks and raw vegetables). The resulting composts
were referred to as the windrow compost (WC), wire mesh compost
(MC), and static compost (SC).
In addition to these three composts, a fourth pile consisting of prepreparation and leftover cooked food organic waste (e.g., rice, beans
and, rarely, meats) was also managed. This compost also followed the
windrow method and was termed the total compost (TC). It was used to
comparatively evaluate the effect of input materials on the final composts. Storino et al. (2016) state that for effective management of organic waste via domestic composting, it is essential that more types of
waste be processed, including those of animal origin. Thus, composting,
387
Journal of Environmental Management 226 (2018) 386–399
J.Z. Lima et al.
2.2.3. Elemental composition
The presence of carbon (C), nitrogen (N) and hydrogen (H) was
determined using a 2400 CHNS Series II Elemental Analyser
(PerkinElmer). A 10-mg amount of each sample was measured on a
PerkinElmer AD-6 Auto Balance Controller microbalance, which was
connected to a 2400 CHNS Elemental Analyser for direct mass acquisition. Samples were compacted into tin capsules, closed, and introduced into the analyser's oven.
The concentrations of Pb, Zn, Cd, copper (Cu), chromium (Cr),
nickel (Ni), iron (Fe), and aluminium (Al) were determined from the
analysis of the compost samples using an Atomic Absorption
Spectrophotometer (Varian AA240FS FS-AAS) as described by Method
B3111 of the Standard Methods for the Examination of Water and
Wastewater (APHA, 2012). The solid samples were digested according
to the 3030F Method of the Standard Methods for the Examination of
Water and Wastewater (APHA, 2012). Digestion was performed with
HNO3 + 50% HCl (3:1 ratio).
The concentrations of phosphorus (P), potassium (K), sulphur (S),
calcium (Ca) and magnesium (Mg) were determined according to the
method described in MAPA (2013). Specifically, the P analysis required
extraction using hydrochloric acid and concentration determination
using the Molybdovanadophosphoric Acid Spectrophotometric Method;
the K analysis required extraction using Hydrochloric Acid and Quantification via Flame Photometry (Digimed DM 32 Flame Photometer); S
was analysed using the Gravimetric Barium Sulphate Method; and the
Ca and Mg analysis required extraction of Ca and Mg with hydrochloric
acid and concentration determination using Atomic Absorption Spectrometry (PerkinElmer Model 1100B Atomic Absorption Spectrophotometer).
whether at a domestic or community scale, may be an alternative to
reusing meat waste, which is a traditional component of municipal solid
waste. In this sense, the authors showed that the presence of meat waste
as raw composting material can improve the physicochemical characteristics and maturity of the compost without significantly affecting
its salinity, pH, and phytotoxicity. The levels of pathogens were low,
indicating that they can be controlled by intensive management and
adequate handling of compost piles.
2.2. Analytical characterization methods
Several different tests were used to adequately characterize the
organic composts, often using several methodologies to better determine their physical and chemical properties. The composts used in
the various tests were air-dried at room temperature (approximately
25 °C), disintegrated with an agate mortar, homogenized (quartered)
and sieved (2 mm).
2.2.1. Physical properties
The main organic compost physical property characterization tests
were grain size analysis, particle density, bulk density, moisture, and
water retention capacity.
Because the compost samples were formed mostly by coarser particles, the grain size analysis of this material consisted only of its dry
sieving, following the guidelines set in the Brazilian soil standard
(ABNT, 2016), which is similar to ASTM (2004).
The particle density was determined according to the Brazilian
standard ABNT (1984). The mass of the entire set (flask, water and
solids) was determined using the pycnometer method at five different
temperatures between 15 °C and 25 °C.
The bulk density was determined via the self-compaction method
(MAPA, 2007), which is specific for substrates in general, using the
action of the compost's own mass in a graduated cylinder, with the set
(cylinder + compost) dropped from a 10-cm height ten consecutive
times.
The moisture content was determined as recommended by Kiehl
(1985) for organic fertilizers following a combined methodology between the ABNT (1986) Brazilian standard (soil specific) and ASTM
(2014) (indicated for peat and organic soils), wherein compost samples
were air-dried (at approximately 25 °C) and subsequently oven-dried at
combined temperatures (60–65 °C, followed by 105–110 °C).
The water retention capacity (WRC) was calculated following the
tension table method, adjusted to a 10-cm water column (10 hPa),
which corresponds to a water fraction readily available to plants, according to the assumptions of MAPA (2007).
2.2.4. Cation exchange capacity (CEC), specific surface area (SSA) and
porosity (Vp and Rp)
The cation exchange capacity (CEC) was obtained via the titrimetric
method, based on the occupation of the organic material's exchange
sites with hydrogen ions from a hydrochloric acid solution and titration
of the acetic acid formed with a standardized NaOH solution, using
phenolphthalein as an indicator, according to the method described in
MAPA (2013). The specific surface area (SSA) was determined via nitrogen physisorption, with the adsorption isotherms acquired in a
Quantachrome NOVA 1000 version 10.02 instrument using the Brunauer-Emmett-Teller (BET) Method. The total pore volume (Vp) was
estimated as the amount of nitrogen adsorbed at the relative pressure of
P/P0 = 0.98. Samples were initially degassed at 200 °C under a N2 flow
for 6 h.
2.2.5. Organic matter (OM) and ash content
The total organic matter (OM) content was calculated using muffle
furnace combustion, a form of direct OM determination that followed a
modification of the specific methodology for organic fertilizers described in Kiehl (1985), with sample drying at 50 °C and at an ignition
temperature of 550 °C in a muffle furnace for 24 h. This differs from the
ABNT, 1996 Brazilian standard (for soils in general) and ASTM (2014)
(for peat and organic soils), which recommend a temperature of approximately 440 °C.
The presence of OM was calculated using the following equation
(Eq. (2)):
2.2.2. Physicochemical properties
The organic composts were characterized physicochemically by
determining the hydrogen potential (pH), potential redox (Eh), and
electrical conductivity (EC).
The pH, Eh and EC were determined according to the method proposed by the Brazilian Agricultural Research Corporation (EMBRAPA,
2011). Solutions were prepared at a 1:2.5 compost:water ratio, i.e., 10 g
of each compost plus 25 mL of deionized water. The samples were
stirred and then allowed to sit for 60 min. Next, the solutions were
filtered using filter paper (with a weight of 80 g m−2 and particle retention of 4–12 μm), and the pH, Eh and EC values were determined
using the appropriate equipment (respectively, glass electrode and Digimed DM21 pH meter; platinum ring electrode and Micronal B374 pH
meter; and an Analyser 7A04 conductivity cell and an Analyser 650
conductivity meter). According to the same methodology, the pH was
determined in potassium chloride (KCl), allowing the calculation of
ΔpH according to Eq. (1):
ΔpH = pHKCl − pHH2 O
Minitial − Mfinal ⎞
OM = ⎛
x 1000
Minitial
⎝
⎠
⎜
⎟
(2)
−1
where OM is the organic matter content (g kg ), and Minitial and Mfinal
are the weight of the compost (g) before and after combustion, respectively.
The ash content (g kg−1) was determination followed the guidelines
presented in ASTM (2014), according to Eq. (3).
ASH = 1000 − OM
(1)
388
(3)
Journal of Environmental Management 226 (2018) 386–399
J.Z. Lima et al.
Fig. 1. Composts grain size distribution curves (a) and moisture and water retention capacity (WRC) of organic composts (b). *Air drying at room temperature,
approximately 25 °C. TC = total compost; WC = windrow compost; MC = wire mesh compost; SC = static compost.
shaken in a horizontal shaker at a speed of 10–20% at room temperature (close to 25 °C). After 24 h of shaking, the extracts were centrifuged
and filtered on filter paper (of a weight of 80 g m−2 and particle retention of 4–12 μm). The physicochemical parameters (pH, Eh and EC)
were controlled with measurements of the initial (immediately after
contact between the compost and the contaminant solution) and final
(after 24 h of contact, immediately after filtration) values. The concentrations of Pb, Zn and Cd present in the filtered extracts were analysed in a PinAAcle 900F Atomic Absorption Spectrophotometer
(PerkinElmer). The calibration curves were built using three different
concentrations obtained from the dilution of the respective PerkinElmer
Standards (ISO 9001 Purity Certification) in deionized water. All calibration curves provided a correlation coefficient higher than 0.995.
Most of the extracts were diluted according to the equipment's quantification limit (0.448, 0.006 and 0.018 mg L−1 for Pb, Zn and Cd, respectively), reaching 1:200 for the Zn and Cd blank solutions.
All experimental results (characterization and adsorption) were
analysed statistically through Pearson correlation matrices using data
combinations.
The thermal degradation of the composts was also analysed by
thermogravimetric analysis (TGA), which allows the determination of
mass loss as a function of the temperature increase, which directly
corresponds to the OM content of the sample. This test was performed
in a TGA/DSC 2 Thermogravimetric Analyser (Mettler-Toledo) with the
following
conditions:
initial
temperature = 30 °C,
final
temperature = 1000 °C, and heating ramp = 10 °C min−1; additionally,
the samples were submitted to synthetic air (50 mL min−1). As background, an empty alumina crucible was used under the same conditions
as the sample.
2.2.6. Fourier transform infrared fluorescence (FTIR)
The analyses were performed in a Fourier Transform Infrared
Spectrophotometer–FTIR (IRAffinity 1, Shimadzu) using the direct
sample transmission method with dilution in potassium bromide (KBr).
Spectra were acquired in the 4000-400 cm−1 range with a resolution of
4 cm−1 and 32 cumulative sweeps.
2.3. Adsorption (batch equilibrium test)
3. Results and discussion
To verify whether the composts can be used in metal adsorption (as
reactive materials), in addition to the detailed characterization, complementary tests must be conducted to evaluate their adsorption potential. Batch equilibrium tests were the method of choice in the present
study.
The batch equilibrium test consisted of promoting the contact of
composts (particles smaller than 2.0 mm, oven-dried for 48 h at 50 °C)
with single-element electrolytic solutions over a predetermined contact
time according to the adaptation of methodologies described in Roy
et al. (1992), ASTM, 2003, Zuquette et al. (2008) and Mohamed et al.
(2017). As such, the intrinsic and individual capacity of each compost
for each metal could be studied without direct competition for adsorption sites. The metal cations Pb2+, Zn2+ and Cd2+ were selected
because they are important and frequent contaminants in metal ore
mining waste. Contaminant solutions were prepared with a concentration of approximately 150 mg L−1 from the respective chloride
salts and deionized water. This concentration was chosen because it
was higher than the values found in the leachate of mining waste in
Ribeira Valley, Brazil, as observed by Raimondi (2014).
One gram of each compost was added to 50 mL of each contaminant
solution (1:50 compost:solution ratio) in 50 mL Falcon tubes and
3.1. Physical properties
The four composts showed a small percentage of fine materials (less
than 1.5%) and a high particle content in the sand fraction, ranging
between 91.26% for MC and 95.33% for TC. The medium and coarse
sand fractions must be emphasized, as they constitute more than 80% of
the samples from all composts (Fig. 1a).
Because all compost samples exhibited less than 5% solid particles
that could pass through a 0.075 mm pore sieve, granulometrically they
are regarded as granular materials. Thus, it is important to assess their
graduation levels. According to Pinto (2002), a material is “wellgraded” when it is composed of grains of varying sizes that consequently and generally yield materials with better engineering behaviours. This stems from the fact that smaller grains occupy the void
space between the larger grains, providing lower compressibility,
greater meshing and greater resistance.
This characteristic was assessed via the uniformity (CU) and curvature (CC) coefficients, which relate to the D10, D30 and D60 diameters,
which are characteristic of each material. The former corresponds to
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Journal of Environmental Management 226 (2018) 386–399
J.Z. Lima et al.
Table 1
Physicochemical parameters of composts.
Parameter
TC
WC
MC
SC
pH in H2O (1:2.5)
ΔpH
Eh (mV)
EC (μS cm−1)
CEC (cmolc kg−1)
SSA (m2 g−1)
Vp (cm3 g−1)
Rp (Å)
6.5 ± 0.0
−0.4 ± 0.1
+347.00 ± 4.58
2200.00 ± 26.00
75.00
9.64
0.04306
89.34
7.4 ± 0.0
−1.0 ± 0.1
+267.67 ± 9.29
664.67 ± 46.69
34.00
5.69
0.03341
117.50
7.7 ± 0.1
−0.9 ± 0.1
+284.33 ± 4.04
708.67 ± 8.14
32.00
13.37
0.05400
80.78
6.4 ± 0.1
−0.9 ± 0.1
+330.00 ± 9.54
157.33 ± 2.31
29.00
62.99
0.01113
35.33
Eh = potential redox; EC = electrical conductivity; CEC = cation exchange capacity; SSA = specific surface area; Vp = total pore volume; Rp = average pore radius;
TC = total compost; WC = windrow compost; MC = wire mesh compost; SC = static compost.
commercial humic material with a predominance of humic acid;
Massukado (2008), who evaluated two Brazilian composts resulting
from organic municipal waste composting in a composting yard and a
municipal garden, reported values of 83.83% and 102.85%, respectively; and Guermandi (2015), who worked with composts obtained
from the composting of municipal organic waste with various compost
heap treatments, reported much larger values – between 352.1% and
534.3%.
the quotient between the diameters with the cumulative percentages of
60 and 10%, whereas the latter corresponds to the quotient between the
square of the diameter with a cumulative percentage of 30% and the
product of the other two diameters (10 and 60%). As expected, the
coefficients obtained were the same for all four composts because the
grain size curves presented similar shapes and a tendency to be parallel
with a small vertical displacement between them (Fig. 1a). Concerning
the CU, all composts showed a value of 3. According to the Brazilian
standard ABNT, 1995, this value corresponds to moderately uniform
materials because values higher than 1 correspond to a reduction in the
grain size curve, increasing the range of grain size variations. Concerning the CC, all composts exhibited a value of 1 and could thus be
classified as well-graded – even if the value corresponded to the lower
limit of this classification (CC between 1 and 3) (Pinto, 2002).
The results for particle density and bulk density were 2.163 and
0.61 g cm−3 for TC; 2.195 and 0.52 g cm−3 for WC; 2.490 and
0.87 g cm−3 for MC; and 2.421 and 0.79 g cm−3 for SC, respectively. As
expected, these two parameters were directly related, and the highest
values belonged to the MC and SC, probably because their composition
was more influenced by the local soil composition during the composting process and because the TC and WC consisted of more decomposed OM with a lower proportion of coarse residues. In fact, mineral soils typically have higher particle density (2.600–2.700 g cm−3)
and bulk density (1.00–1.80 g cm−3) values than do organic soils (bulk
density between 0.80 and 1.00 g cm−3) (Don Scott, 2000).
Fig. 1b shows the variations in moisture content in the analysed
organic composts as a function of the drying temperature. Generally,
the resulting total moisture values for TC and WC were similar and
higher than those for MC and SC, which were also similar. Clearly,
water is primarily bound in a simple way to the solid particles in
composts – more than 90% of the net fraction present in each compost
was lost naturally merely by drying at room temperature.
Regarding the water retention capacity (WRC) (Fig. 1b), this parameter was analysed for the samples submitted to a 10 hPa pressure. This
analysis is important – especially from the perspective of using these
organic materials as substrates – because it generally refers to a
moisture content close to the field capacity, corresponding to the water
readily available for plants. Similar to the total natural moisture values,
the TC (54.93%) and WC (65.26%) exhibited the highest WRC, whereas
the MC (22.75%) and SC (43.43%) exhibited the lowest WRC. Moreover, unlike the other composts studied, the WRC of the MC was very
close to its natural total moisture content. However, the other three
composts could retain more water in addition to their respective natural
moisture, with a limit close to their WRC, at the given tension value.
For comparison, a Brazilian peat analysed by the same methodology
presented an intermediate WRC of 36.28% (Lima, 2017) (larger than
the MC but smaller than the TC, WC, and SC). Some authors who used a
simpler system (consisting of filter paper conditioned on a funnel
placed over an Erlenmeyer flask) obtained the following WRC results:
Melo et al. (2008), who studied various organic matrices, reported
values of 81 ± 1.8% for a commercial compost and 63 ± 5.1% for a
3.2. Physicochemical properties
Unlike other organic reactive materials, such as peat, compost pH
varies from neutral to basic ranges. Valente et al. (2009) state that
numerous chemical reactions occur during the composting process,
regulating the acidic condition and leading to the generation of a final
product with a pH varying between 7.0 and 8.5.
According to Table 1, TC and SC composts presented similar pH
values (6.5 ± 0.0 and 6.4 ± 0.1, respectively). These values classify
them as slightly acidic. However, the WC and MC composts presented
higher pH values (7.4 ± 0.0 and 7.7 ± 0.1, respectively) and were
thus classified as slightly alkaline. Generally, all composts oscillated
close to neutrality, which indicates their maturity (Epstein, 1997;
Valente et al., 2009).
For comparative purposes – and barring any peculiarities in the
composting methodologies and the methods adopted for measuring the
pH in water – the values found herein agree with those of the composts
derived from the organic fraction of MSW described in the literature,
whose pH commonly varies between 5.0 and 8.7 (Barreira, 2005;
Farrell and Jones, 2010a; Simantiraki et al., 2013; Guermandi, 2015;
Venegas et al., 2015; Onwosi et al., 2017). Moreover, the values are
within the range recommended for use as a growth medium (6.0–8.0)
(WRAP, 2014).
The pH value is a fundamental factor in PTE chemical equilibrium
kinetics, with an undeniable influence on adsorption, as it affects the
functional groups present at the adsorbent's surface, the PTE ionization
state, and the solubility of the formed complexes. The CEC of organic
composts strongly depends on pH, indicating that their surface charge
derives from reactions occurring at the adsorbent-solution interface. In
general, for most PTE (e.g., Pb, Zn, Cd, and Cu), alkaline conditions
favour their immobilization (Weber, 1972; Kabata-Pendias and Pendias,
1984; Yong and Mulligan, 2004). The pH values of the composts studied
herein (neutral or slightly alkaline) favour their use as reactive materials, even if there is an optimum adsorption pH for each metal.
All composts presented pH values in KCl lower than those obtained
in water. Thus, all composts exhibited negative ΔpH values, ranging
between −0.4 ± 0.1 for TC to −1.0 ± 0.1 for WC (Table 1). As the
ΔpH allows an estimation of the net surface charge balance of the
material, negative values may indicate a predominance of negative
charges at the particle surfaces (Mekaru and Uehara, 1972), favouring
the retention of metallic cations. This feature may be an additional
benefit to using these composts in the adsorption of metallic ions (such
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J.Z. Lima et al.
Fig. 2. Elemental composition in relation to the presence of C, H, N and C/N, H/C ratios of organic composts (a); Organic matter (OM) and ash contents in composts
(b); TGA curves for organic composts (c) and Infrared spectra for all organic composts (d); TC = total compost; WC = windrow compost; MC = wire mesh compost;
SC = static compost.
as Zn2+, Pb2+ and Cd2+).
One other physicochemical property of these composts was measured: the Eh, which evaluates electron transfer (donation or receipt).
Because these materials show a high organic matter content, this fraction may be regarded as the main electron source, and it is controlled by
aeration and biological reactions (Fageria and Stone, 2006). Table 1
presents that the Eh of WC (+267.67 ± 9.29 mV) and MC
(+284.33 ± 4.04 mV) were similar, as were the values of TC
(+347.00 ± 4.58 mV) and SC (+330.00 ± 9.54 mV). All composts
are found to be under oxidizing conditions, contributing favourably to
metal immobilization because several metals become directly or indirectly soluble under reducing conditions (Kabata-Pendias and
Pendias, 1984). Alterations in the Eh of soils and reactive materials can
affect the oxidation state of several elements, such as arsenic (As), selenium (Se) and chromium (Cr), with consequent changes in speciation,
solubility and toxicity. However, other metals, such as Pb, Cu, Zn and
Ni, although their oxidation states remain unchanged, can be indirectly
influenced because they are strongly bound to Fe and manganese (Mn)
oxides, which are susceptible to changes in oxidation potential – under
reducing conditions, they become more soluble, making the adsorbed
metals available.
Another physicochemical parameter evaluated was the EC, which
directly measures the electric current conduction of the aqueous solution and is associated with the presence of dissolved salts. The temperature, total concentration and valence of ions influence this parameter (Lima, 2014). The TC had an EC (2200.00 ± 26.00 μS cm−1)
considerably
higher
than
that
of
all
other
composts
(157.33 ± 2.31–708.67 ± 8.14 μS cm−1) (Table 1). This result is
probably due to the raw material that was composted for the generation
of the TC – raw fruit and vegetable residues, plus leftovers of processed
and cooked foods that probably had been seasoned – increasing the
salinity of the final material. Nonetheless, the SC revealed the lowest
EC.
3.3. Cation exchange capacity (CEC), specific surface area (SSA) and
porosity (Vp and Rp)
Throughout the composting process, as humus is formed – the
component related to cationic nutrient adsorption – the CEC of the
organic waste increases. Humus is an electronegative colloid (Kiehl,
2004), and the greater the humification of OM is, the greater the CEC is.
This is because the organic fraction contains particles with negatively
charged surfaces, attracting cations. This negative charge is mostly attributable to the ionization of COOH groups, with some contribution of
OH and NH phenolic groups. Unlike clay minerals, the capacity of OM
to bind exchangeable cations is not fixed, as the degree of acidity of
humic substances varies widely, and the CEC strictly increases with pH.
The latter result may be attributable to the higher ionization degree of
acidic groups (especially COOH) that occurs at higher pH levels
(Stevenson, 1982). Thus, organic composts with high OM are expected
to exhibit high CEC. However, the OM content is not the sole factor
influencing CEC because TC exhibited the greatest CEC (75.00 cmolc
kg−1)
but
only
the
second
largest
OM
content
(376.17 ± 41.64 g kg−1). This finding may be related to the differing
OM humification degrees, which is directly related to the CEC. The WC,
MC and SC had similar CEC values (29.00–34.00 cmolc kg−1) (Table 1).
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J.Z. Lima et al.
Ca, Mg and S concentrations of other Brazilian and international
composts obtained from MSW or organic residue. A comparative analysis concludes that the composts obtained herein showed lower concentrations of these elements compared to data in the existing literature, with particular emphasis on K and Ca. For instance, K reached
values of 6.31–32.20 g kg−1 in the literature, whereas it did not exceed
2.00 g kg−1 in the four composts obtained in the present study. Similarly, Ca concentrations were above 20.00 g kg−1 in the comparison
composts.
According to Kiehl's classification (1985) regarding the range of
values for organic fertilizers with natural moisture, the concentrations
of all analysed elements (P, K, Ca, Mg, and S) for all composts can be
categorized as low for possible agricultural use (P below 2.18 g kg−1; K
below 4.15 g kg−1; Ca below 15.00 g kg−1; Mg below 6.00 g kg−1; and
S below 2.00 g kg−1), with the exception of P in TC and Ca in TC and
WC, whose concentrations are average (P between 2.18 and 6.55 g kg−1
and Ca between 15.00 and 30.00 g kg−1). This result does not favour
plant growth, for instance, when using these composts as a vegetable
cover system in a mining ore disposal region.
The total concentrations of Zn, Cu, Fe and Al are shown in Table 2.
The TC exhibited the largest concentrations of Zn (132.80 mg kg−1) and
Cu (12.80 mg kg−1), whereas SC contains the largest concentrations of
Fe (27,190.00 mg kg−1) and Al (37,520.00 mg kg−1). In contrast, MC
exhibited the lowest concentrations of Zn (50.60 mg kg−1) and Cu
(< 0.30 mg kg−1), whereas WC showed the lowest concentrations of Fe
(14,660.00 mg kg−1) and Al (22,170.00 mg kg−1). Table 2 presents the
concentrations of these elements (Zn, Cu, Fe and Al) in other Brazilian
and international composts derived from MSW or organic residues. The
Zn concentrations of the four composts obtained herein agree with the
data in the literature, particularly with that of Massukado (2008). Cu
concentrations varied considerably in the comparison composts; the TC,
WC, MC and SC concentrations of this element can be considered low.
The analysed composts also showed high concentrations of Fe and Al,
arising primarily from the composted organic matter.
Total concentrations of PTE (Pb, Cd, Cr and Ni) are displayed in
Table 2. The SC exhibited the highest concentrations of Pb
(21.00 mg kg−1) and Ni (1.70 mg kg−1). The WC revealed the lowest
concentrations of Pb (3.00 mg kg−1), Cd (< 0.06 mg kg−1) and Ni
(< 0.80 mg kg−1), which can be an advantage for this type of compost.
Table 2 summarizes the concentrations of Pb, Cd, Cr and Ni in other
Brazilian and international composts arising from MSW and organic
residue. The metal concentrations demonstrated a wide range of variation; the four composts studied herein showed low concentrations of
these elements, but they remained within the typical range for these
types of compost.
The high concentrations of Pb, especially in Farrell and Jones
(2010a) and Simantiraki et al. (2013) are emphasized, suggesting the
need for a follow-up and a more detailed analysis to understand how
this Pb was assimilated into the compost: either through the initial
substrate or during the composting process. It is desirable to avoid the
assimilation of these contaminants for potential use in the environment.
Benson and Othman (1993) found dangerous and undesirable constituents in compost leachates, with some metals exceeding standards.
Huerta-Pujol et al. (2010) observed high PTE concentrations in the
plastic bags used to collect the organic fraction of MSW, which may
migrate to the compostable matrix. Farrell and Jones (2010b) evaluated
some parameters pertaining to green waste and catering waste used as
feedstock materials in composting, finding dry basis Pb concentrations
of 51.90 ± 6.90 mg kg−1 and 4.30 ± 1.90 mg kg−1, respectively.
Huerta-Pujol et al. (2011) compared the mineral composition of the
organic fractions obtained from an ordered collection with segregation
at the source and from a mechanical separation of MSW collected as a
whole. The results revealed larger nutrient (P, K, Na, Ca, Mg, Fe and
Mn) and significantly lower PTE (Zn, Cu, Ni, Cr, Pb and Cd) contents in
the array from the compostable organic fraction segregated at the
source compared to the organic fraction collected as a whole, which
In comparison with other studies on composts from different sources
(MSW or organic waste), CEC values ranged between 19.40 cmolc kg−1
(Massukado, 2008) and 105.00 cmolc kg−1 (Venegas et al., 2015), with
a larger prevalence of values closer to the lower limit. The studied
composts have values above 29.00 (cmolc kg−1).
Valente et al. (2009) argued that the humic substances that form the
compost are colloids that present a high SSA, which increases with the
porosity of the medium and correlates inversely with the size of the soil
particles or reactive material. The higher the SSA is, the higher the
adsorption capacity is, because the potential to develop surface loads
also increases (Weber, 1972). The SC showed the highest SSA
(62.99 m2 g−1), which correlates with the higher presence of fine particles (clay, silt, and fine sand) and smaller pores (Rp = 35.33 Å) among
all composts. However, despite the small pore size, SC had the smallest
CEC value (29.00 cmolc kg−1), possibly due to its pore volume
(Vp = 0.01113 cm3 g−1) being the lowest of all composts.
3.4. Elemental composition
According to the data presented in Fig. 2a, C is the most abundant
element in the composts, followed by H and N. The lower average values for C, H and N were obtained for MC (C = 3.63%, H = 0.79%,
N = 0.36%), whereas the highest values were found for the TC
(C = 10.15%, H = 1.72%, N = 1.06%).
The calculation of the C/N and H/C ratios (Fig. 2a) showed that the
former varied between 9.58 ± 0.19 (TC) and 13.07 ± 0.85 (WC). The
latter varied between 0.16 ± 0.03 (WC) and 0.22 ± 0.00 (MC). Kiehl
(1985) states that the C/N ratio is an indicator of the degree of decomposition of composts: the lower the value of this ratio is, the higher
the decomposition is. Furthermore, smaller H/C ratios indicate a higher
degree of aromaticity, which is also characteristic of more decomposed
structures. Therefore, as the TC compost presented the lowest C/N ratio
and one of the lowest H/C ratios (Fig. 2a), there was a higher degree of
decomposition in relation to the other composts.
Kiehl (1985) noted that a C/N ratio between 8 and 12 indicates a
cured fertilizer with great agricultural potential. All analysed composts
fit in this category, except for the WC, although its C/N ratio was close
to its upper limit.
Several studies made additional comparative data of C and N levels
and their consequent C/N ratios for Brazilian and international composts. Faverial et al. (2016) observed that final compost quality was
affected by weather conditions. Composts produced under a tropical
climate presented high losses of carbon and nutrients during composting, inducing lower organic matter and nutrient contents than those
of temperate composts. In this respect, the C and N contents of the
composts studied herein (tropical composts) were low, yielding lower
C/N ratios, in agreement with those calculated by Massukado (2008)
(tropical composts with C/N ratios varying between 8.30 and 12.75)
and Simantiraki et al. (2013) for mature composts (temperate composts
with C/N between 22.00 and 24.00). The data still fit in the wide C/N
ratio variation range found for Brazilian composting facilities
(14.15–40.72), in tropical climates (Barreira, 2005). On the other hand,
the temperate composts (Farrell and Jones, 2010a; Simantiraki et al.,
2013–fresh composts; Venegas et al., 2015) mostly showed higher C
contents (between 24.60 and 31.00), N contents (between 0.97 and
1.80) and, C/N ratios (between 15.00 and 25.00) in relation to the
tropical composts of this study.
The total concentrations of cationic (K, Ca and Mg) and anionic (P
and S) macronutrients on a dry basis in an oven at 65 °C are displayed in
Table 2. The TC presented the highest concentrations of P (2.31 g kg−1)
and S (1.30 g kg−1) and the lowest concentration of Mg (0.20 g kg−1).
The WC exhibited the largest concentrations of Ca (28.60 g kg−1) and
Mg (1.30 g kg−1) and a lower S content (0.3 g kg−1). The MC showed
the highest K (1.99 g kg−1) and Mg (1.30 g kg−1) concentrations and
the lowest Ca (6.40 g kg−1) concentration. Finally, SC had the lowest P
(1.35 g kg−1) and K (0.66 g kg−1) values. Table 2 also provides the P, K,
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Journal of Environmental Management 226 (2018) 386–399
J.Z. Lima et al.
Table 2
Concentration of various elements found in organic composts from the present study1 and from other Brazilian2 and international3 studies.
Elements
TC1
WC1
MC1
SC1
Massukado2 (2008)
Farrell and Jones3
(2010a)
Simantiraki et al.3
(2013)
Guermandi2 (2015)
Venegas et al.3
(2015)
P (g kg−1)
K (g kg−1)
Ca (g kg−1)
Mg (g kg−1)
S (g kg−1)
Cu (mg
kg−1)
Fe (mg
kg−1)
Al (mg
kg−1)
Zn (mg
kg−1)
Pb (mg
kg−1)
Cd (mg
kg−1)
Cr (mg
kg−1)
Ni (mg
kg−1)
2.31
1.33
16.40
0.20
1.30
12.80
2.01
1.58
28.60
1.30
0.30
3.80
2.01
1.99
6.40
1.30
0.50
< DL
1.35
0.66
11.20
0.90
0.40
1.90
2.72–5.85
6.31–12.88
22.57–32.88
1.99–3.91
2.14–3.15
16.20–57.76
0.90 ± 0.20
10.10 ± 0.60
51.80 ± 5.30
ND
ND
329.00 ± 83.00
ND
ND
ND
ND
ND
126.15–1269.14
17.05–20.22
26.40–32.20
34.48–180.00
3.04–5.41
ND
12.40–29.20
9.43
10.53
99.27
9.11
6.17
168.00
16,390.00
14,660.00
23,430.00
27,190.00
25,240.00–33,270.00
ND
ND
2072.00–3344.00
9660.00
25,260.00
22,170.00
31,780.00
37,520.00
ND
ND
ND
ND
18,240.00
132.80
54.01
50.60
55.80
49.50–147.18
505.00 ± 216.00
218.81–1697.00
119.60–155.60
523.00
11.00
3.00
6.00
21.00
< 1.00–23.00
906.00 ± 324.00
77.52–774.53
12.00–131.60
89.00
1.30
< DL
< DL
0.50
< 0.50- < 1.00
ND
< DL
< 0,04
2.90
1.80
5.90
6.10
4.50
< 0.50–31.10
48.10 ± 13.30
38.45–258.72
2.00–23.20
ND
1.60
< DL
< DL
1.70
< 0.50–2.10
87.20 ± 19.20
19.49–203.15
26.00–48.00
40.00
< DL = below the detection limit (In this study: < 0.30 mg kg −1 for Cu; < 0.06 mg kg−1 for Cd; < 0.80 mg kg−1 for Ni); ND: not determined; TC = total compost;
WC = windrow compost; MC = wire mesh compost; SC = static compost.
Stevenson (1982) states that relating mass loss and temperature in
humic acids reveals two main moments: one at a relatively low temperature (approximately 280 °C) and another at a higher temperature,
above 400 °C. Regarding the composts (Fig. 2c), in the first stage
(temperature < 250 °C), mass loss may be related to the evaporation of
adsorbed water and primary degradation, which is associated with the
primary volatile loss and the disruption of carbohydrates, the thermal
decarboxylation of acid groups, hydroxylated aliphatic structure dehydration, and the generation of low molecular weight alcohols. In the
second stage (250 °C < temperature < 500 °C), the decoupling and
the collapse of aromatic structures present in the humic material may
occur; the organic constituents may be, in fact, transformed into volatile and mineral residues. In the third stage (temperature > 500 °C),
practically all alicyclic carbon structures may have been broken down
(Sheppard and Forgeron, 1987; Bernabé, 2008; Di Nola et al., 2010;
Adewuyi and Pereira, 2017).
Because the chemistry of PTE and reactive materials is directly related to the formation of complexes with OM, this parameter acquires
an unequivocal importance in contamination cases. Therefore, the
higher OM content found in the WC can be regarded as an indication of
its greater potential for metallic cation immobilization. For monovalent
cations such as sodium (Na+) and K+, cationic exchange occurs primarily through the formation of simple salts with COOH groups
(RCOONa, RCOOK) present in the organic portion. Multivalent cations
(e.g., Cu2+, Zn2+, Mn2+ and cobalt, Co2+) may establish coordinated
bonds with organic molecules (Stevenson, 1982). Local environmental
conditions regulate the behaviour of Cd in soil, but in general, this
metallic cation binds strongly to OM, becoming mostly immobilized
(ATSDR, 2012). The fixation of Pb by organic matter is more important
than carbonate precipitation or hydrated oxide sorption because the
majority of Pb in soil will be directly bound to OM, mostly through
ionic exchange (Adriano, 1986). Pb is characteristically found in the
vicinity of the soil surface in most profiles, primarily arising from the
accumulation of OM (Kabata-Pendias and Pendias, 1984). Likewise, Zn
accumulation at the surface stems from its assimilation by the roots of
deeper horizon plants and the decomposition of OM, with consequent
immobilization at the surface (Adriano, 1986). Moreover, soil organic
matter is known for its high ability to promote Zn binding, forming
stable compounds. Hence, Zn leaching from soil is difficult, with its
accumulation being observed in peat and organic horizons. However,
may have favoured the migration of metals in compostable materials. In
addition, Montejo et al. (2015) showed the percentage of inert impurities with a size larger than 2 mm (such as plastic or glass) greatly
exceeded the legal limit for some composts with a separation process in
MBT (Mechanical and Biological Treatment) plants. Guermandi (2015)
described a large Pb variation (12.00–131.60 mg kg−1) in final composts as a function of the composting pile typology.
Regarding the application of compost in natural environments, one
must consider the presence of PTE (and other chemical and biological
agents) in the compostable waste, such as the organic fraction of MSW,
which may accumulate in the environment and affect biota and human
health (Domingo and Nadal, 2009; Valente et al., 2009; Cerda et al.,
2017).
The maximum contents for some metals (Pb, Cd, Cr, Ni, and Zn) in
fertilizers according to the specific regulations of some countries are
available in the Supporting information (Table S1). Brazil specifies that
this applies to organic fertilizers, whereas the European Union refers to
“soil improvers”. Comparing the legislative values, all composts analysed herein could be used in agriculture, with the exception of the TC
(Table 2), which fails the European and Australian criteria for Cd. This
favours their use as reactive materials for barriers – although this serves
a different purpose from that presented in the standard, it also constitutes an environmental application, with direct contact with the
ground and the surrounding ecosystem.
3.5. Organic matter (OM) and ash content
The composts showed varying levels of organic matter (Fig. 2b),
with the WC and MC exhibiting the highest and lowest mean values
(418.70 ± 24.21 g kg−1 and 193.92 ± 21.70 g kg−1, respectively).
The presence of OM was similar in TC and WC, with the latter exhibiting a darker brown colour, characteristic of OM in an advanced
state of decomposition.
The thermal degradation of the main compost constituents is presented in Fig. 2c. Similar to other organic materials such as peat
(Sheppard and Forgeron, 1987), biomass (Di Nola et al., 2010) and the
sponge Luffa cylindrica (Adewuyi and Pereira, 2017), one can distinguish three different stages in this process, with the degradation and the
thermochemical conversion of the constituents present, including cellulose and lignin, varying only partly in the temperature limits. In fact,
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J.Z. Lima et al.
The Pb, Zn and Cd adsorption results in conjunction with the pH-Eh
diagrams (Takeno, 2005) indicate that the contaminants are mostly
found as bivalent ions (Pb2+, Zn2+ and Cd2+), as expected. The variation in EC (Fig. 3c) in solutions with composts and the contaminants
Pb, Zn or Cd was wide. All samples showed increasing EC post-contact
time, with the TC exhibiting the largest change in every case. In fact,
and as mentioned earlier, the TC presented the highest intrinsic EC as a
consequence of the input material. Generally, this increase in conductivity values can be associated with the cation exchange mechanism,
with the release of previously adsorbent surface-adsorbed cations and
the subsequent binding of the metal cations in solution, and the release
of elements present in the organic and inorganic matrices of the composts. The contaminant blank solutions showed a clear, direct influence
on the EC of samples containing compost and contaminant solution. For
example, the Zn blank exhibited the largest EC of all blanks, and the
samples containing compost and Zn also had the highest EC compared
to all other samples containing compost and Pb or Cd. Likewise, the
compost blanks (compost + deionized water) exhibited the lowest EC
values, which was expected due to the low conductivity of water (mean
5.00 μS cm−1).
the stability constants of Zn-organic matter complexes are relatively
low (Kabata-Pendias and Pendias, 1984; WHO, 2001). Acidic and sandy
soils with low OM contents have a reduced Zn adsorption capacity
(WHO, 2001).
3.6. Fourier transform infrared fluorescence (FTIR)
An FTIR analysis provides information on the structural and functional characteristics of reactive organic materials. The resulting characteristic bands for each organic compost (Fig. 2d) were similar to those
of the humic and fulvic substances reported in Swift (1996) and
Silverstein et al. (2005). All composts yielded similar infrared spectra;
there were a few variations in transmittance for TC, but its peaks were
located at similar wavenumbers. Changes in spectral magnitude cannot
be compared directly but may indicate some variations among the
composts. Fig. 2d shows a characteristic band at 3400 cm−1 that may
be attributed to the stretching of OeH bonds of phenolic groups. Bands
at 2930 and 2840 cm−1 are ascribed to asymmetrical and symmetrical
CeH bond stretching, respectively. One other intense band occurs in
the 1600 cm−1 region, probably related to C]C aromatic stretching or
asymmetrical COO− stretching. All materials exhibited a band at
1380 cm−1 (sharper in TC), which was related to the symmetrical
COO− stretching and/or folding of aliphatic CeH bonds. Finally, the
band in the 1040 cm−1 region may be associated with aliphatic CeC
bond stretching (Swift, 1996; Silverstein et al., 2005).
3.7.2. Analysis of the Pb, Zn and Cd adsorption capacity of the organic
composts
The metal ions have different adsorption preferences (Sparks,
1995), as illustrate in Fig. 4 by the different PTE adsorption capacities
of the four composts according to the metal of interest (Pb, Zn and Cd).
This probably explains the greater percentage of Pb adsorption compared to other metals (Zn and Cd). The removal of Pb was very similar
among all composts (94.0–99.6%), in accordance with the batch model
experimental condition in Paradelo and Barral (2012). Their results
exhibited nearly 100% Pb removal at all initial concentrations tested
(using compost obtained from the organic fraction of MSW, provided by
an industrial composting). The major variations occurred for the Cd
(55.4–89.8%) and Zn (22.1–64.0%) removal capacities (Fig. 4). More
specifically, with regard to each compost, there was a higher removal of
Cd in relation to Zn. Similarly, Simantiraki and Gidarakos (2015)
conducted a series of batch experiments with variation of contact time,
the results of which estimated a more than 90% and up to 80% removal
of Cd and Zn, respectively (using compost sample produced from the
organic matter of MSW with daily cleaning, sieving, stirring and 8
months of maturation).
For Cd and Zn, the WC had a greater adsorption capacity than the
others composts, although the differences were less than an order of
magnitude (Fig. 4). Organic matter has been shown to be an important
factor affecting the retention and mobility of PTE in soil and composts
(Freeze and Cherry, 1979; Sposito, 1989; Sparks, 1995). This is due to
the elevated specific surface and the high presence of carboxyl, amine
or phenolic hydroxyl groups on the surface, which can form stable
complexes with PTE. In addition, other compounds, such as iron and
aluminium oxides and carbonates, may be present in the composts,
contributing to sorption (Epstein, 1997; Paradelo and Barral, 2012;
Obiri-Nyarlo et al., 2014). Therefore, as the composts characteristics
generated from the different composting methods were different (such
as pH, CEC, SSA, in Table 1; C/N and OM in Fig. 2) this would be
expected to interfere with the adsorption potentials. Initially, the
composts generated by windrow composting (WC and TC) seem to
present better adsorption performances for the elements studied.
One may evaluate the relative affinity of PTE cations for an adsorbent (Sparks, 1995). In general, the metal removal trend was
Pb > Cd > Zn for each compost. This adsorption affinity order had
already been reported for MSW-derived composts studied by Paradelo
and Barral (2012); Simantiraki and Gidarakos (2015). A hypothesis
proposed by McKay and Porter (1997) correlates the adsorption affinity
with electronegativity; there is a greater attraction towards the adsorbent surface by more electronegative metal ions. The order of electronegativity (Pb2+ = 1.8 > Cd2+ = 1.7 > Zn2+ = 1.6) and affinity
3.7. Adsorption (batch equilibrium test)
3.7.1. Pre- and post-contact analysis of physicochemical parameters (pH,
Eh and EC)
The pH is directly related to adsorption mechanisms because it affects the surface charges of adsorbents and the speciation of ionic
species in solution. However, this behaviour is influenced by the type of
adsorbent and the contaminant of interest, with adsorption mechanisms
typically operating concurrently. In this sense, the pH increased in all
four composts in the presence of Pb and Cd single-element solutions
after 24 h of contact (Fig. 3a). Sharma and Forster (1993) and Franchi
(2004) also observed a similar increase in pH throughout the adsorption
process in peat, ascribing this finding to the possible release of hydroxyl
ions and/or the removal of hydrogen ions by the adsorbent as a function of metal cation adsorption, respectively. In turn, Higashikawa et al.
(2016) attributed the pH increase observed in their study of the adsorption of animal and plant biochars to the release of alkali salts from
the organic matrix. In contrast, the contact with the Zn solution resulted
in a decrease in pH values after 24 h of stirring, which may indicate a
predominance of cation exchange, with the deprotonation of the functional groups at the surface (releasing more H+ ions to the solution)
with a subsequent increase in sites available for adsorption (Bartczak
et al., 2015). The electrostatic attraction mechanism of the surface
negative charges (as indicated by the negative ΔpH), and the physical
adsorption associated with porosity (SC presented the smallest pores
and the highest Pb adsorption capacity), may also be involved in Pb, Zn
and Cd adsorption. The blank contaminant solutions revealed increasing pH values, with Cd < Pb < Zn. The blank compost samples
(compost + deionized water) showed pH values slightly higher than
that of deionized water.
The potential redox values (before and after contact with the contaminants, Pb, Zn and Cd), indicated dominant oxidizing conditions,
with Eh values after 24 h of contact lower than the initial values, which
may be related to an adsorption equilibrium (Fig. 3b). Compared to the
blanks, there is an unequivocal influence of solutions containing composts and contaminants because the first three plots show that the initial Eh values of compost + contaminant solution are similar to those
of the corresponding blank solutions. The compost blank samples
(compost + deionized water) showed similar but slightly lower Eh
values than that of deionized water.
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J.Z. Lima et al.
Fig. 3. Initial and final pH (a), Eh (b) and EC (c) values for the four composts with Pb, Zn, Cd and water (batch equilibrium test). TC = total compost; WC = windrow
compost; MC = wire mesh compost; SC = static compost; Blank solution = single-element solution (Pb, Zn or Cd + deionized water); TCB, WCB, MCB or
SCB = compost blank sample (TC, WC, MC or SC + deionized water).
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J.Z. Lima et al.
Fig. 4. Comparative analysis of the adsorbed and non-adsorbed concentrations (in equilibrium) of Pb, Zn, and Cd by the organic composts. The numbers in the bars
indicate the percentages of adsorption in relation to the respective initial concentrations. Experimental conditions: temperature 25 °C, equilibrium time 24 h, mass to
volume ratio 1/50 g/mL. TC = total compost; WC = windrow compost; MC = wire mesh compost; SC = static compost.
Table 3
PTE (including Pb, Zn and Cd) adsorption affinity order by organic reactive materials.
Reactive material
Metal ion affinity order
Reference
Peanut husks carbon
Sugar beet pulp
In natural tropical peat (Brazil)
Treated tropical peat (Brazil)
Cellulose/chitin beads
Sphagnum temperate peat (Sweden)
Untreated coffee husks
Tobacco dust
Mango peel waste
Grafted copolymerization-modified orange peel
Phyllostachys pubescens biochar
Old sugarcane bagasse steam activated biochar
Pb > Cd > Ni > Zn
Pb > Cu > Zn > Cd > Ni
Pb ≫ Cu > Cd ≈ Zn ≈ Mn
Pb > Cu > Mn > Cd > Zn
Pb > Cd > Cu
Pb > Cu > Ni > Cd > Zn
Cu > Cr > Cd > Zn
Pb > Cu > Cd > Ni ≈ Zn
Pb > Cd
Pb > Cd > Ni
Pb > Cd
Cd > Cu > Pb
Ricordel et al. (2001)
Reddad et al. (2002)
Franchi (2004)
Zhou et al. (2004)
Kalmykova et al. (2008)
Oliveira et al. (2008)
Qi and Aldrich (2008)
Iqbal et al. (2009)
Feng et al. (2011)
Zhang et al. (2017)
Hass and Lima (2018)
compost characterization, positive correlations were found between
ΔpH and CEC, with all ΔpH values being negative, indicating the major
presence of particles with negatively charged surfaces, which undoubtedly favours cation exchange, and between OM and WRC because
organic matter has a known water retention potential; C, H and N were
shown to be closely related, and SSA correlated positively with the fine
particle contents and negatively with Rp because particles with smaller
diameters tend to exhibit larger surface areas and smaller pores. Concerning metal retention, the Zn and Cd removal percentages had similar
correlations with one another and both were different from the Pb removal percentage for all characterization parameters, which suggests
that different adsorption mechanisms predominate in the immobilization of the metals studied (with a possible similarity between the
were the same, confirming these assumptions. Table 3 shows that this
affinity ranking has also been determined for several other organic
reactive materials, except for two cases where Zn and Cd (Reddad et al.,
2002) and Cd and Pb (Hass and Lima, 2018) exchanged positions.
3.8. Statistical analysis
The correlation matrix (Table 4) presents the correlation coefficients calculated to relate several parameters (2 × 2) pertaining to the
physical and chemical characterization of every organic compost with
Pb, Zn and Cd adsorption parameters. Correlations were considered
highly positive for values above 0.9000 (marked in green) and highly
negative for values below −0.9000 (marked in red). Regarding
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Journal of Environmental Management 226 (2018) 386–399
1
−0.5041
−0.5324
1
−0.7499
0.9297
0.9402
1
0.9995
1
mechanisms that govern Zn and Cd retention). Moreover, this hypothesis is corroborated by the finding that Pb adsorption had a negative
correlation with pH and a positive correlation with the clay and silt
fractions, contrary to what was observed for Zn and Cd. Likewise, the
percentages of Zn and Cd removal showed a highly negative correlation
with the SSA and a highly positive correlation with Rp, again contrary
to what was observed for Pb. In fact, Alloway and Ayres (1997) report
that Pb, in general, tends to be adsorbed more strongly, whereas Zn and
Cd are usually more weakly adsorbed, implying greater bioavailability
for the latter two metals. Furthermore, Pb presents a high affinity towards OM (Ribeiro-Filho et al., 2001), whereas Zn and Cd occur mostly
as non-complexed cations in solution (McBride et al., 1997).
4. Conclusions
The potential use of organic composts as low-cost reactive materials
for adsorption of PTE have been evidenced in this study by a combination of characterization and adsorption data. The removal of Pb by all
composts exceeded 90.0% and the highest adsorption capacity of Pb
belonged to the static compost (99.6%), possibly due to the larger
specific surface area (62.99 m2 g−1) and the greater presence of micropores (Rp = 35.33 Å). The highest Cd (89.8%) and Zn (64.0%) adsorption capacities were observed for the windrow compost, and were
very similar to those of the total compost, which is likely due to the
higher amount of organic matter content in both materials (418.70 and
376.17 g kg−1, respectively).
Moreover, the joint statistical evaluation of the characterization and
adsorption results revealed that the Zn and Cd adsorption mechanisms
are similar, and both differ from that of Pb, which is strongly influenced
by adsorbent microporosity.
Therefore, it is concluded that composts derived from the organic
fraction of MSW are promising adsorbent materials, particularly of
metals from mining waste – in the present case, Pb, Zn and Cd.
Nonetheless, this study highlights the need for future research on assessing traditional composting methodologies for generating high
quality humificated organic matter in composts for applications aside
from classic agricultural use: the adsorption, as well as the stability and
desorption potential of these materials, the long-term behaviour and
the environmental risk.
OM = organic matter; CEC = cation exchange capacity; WRC = water retention capacity; C = carbon; H = hydrogen; N = nitrogen.
SSA = specific surface area; Vp = total pore volume; Rp = average pore radius; A% = percentage adsorbed in relation to the initial concentration.
1
0.9821
0.9286
−0.1438
−0.3261
0.2646
0.4368
0.5465
0.5190
1
0.1266
0.5094
0.5873
0.7693
−0.4984
0.4765
0.2745
0.0403
0.5628
0.5494
1
0.2797
0.9532
0.1555
0.5997
0.7083
0.8537
−0.2251
0.2090
0.0226
0.3402
0.3674
0.3464
Clay +Silt
pH
Δ pH
OM
CEC
WRC
C
H
N
SSA
Vp
Rp
A% (Pb)
A% (Zn)
A% (Cd)
1
−0.7665
0.0351
−0.5023
−0.2601
−0.1586
0.0378
0.1547
0.0546
0.9653
−0.8025
−0.9411
0.9115
−0.8139
−0.8326
1
−0.5508
−0.0723
−0.2788
−0.3244
−0.6397
−0.7447
−0.6817
−0.5925
0.6938
0.5684
−0.9613
0.2585
0.2902
1
0.3590
0.9185
0.8087
0.6949
0.6485
−0.5874
0.0292
0.7600
−0.1452
0.8717
0.8603
1
0.8698
0.7647
0.6354
−0.2254
−0.3677
0.4831
0.1702
0.6069
0.5888
1
0.9688
−0.0547
−0.3370
0.1250
0.5466
0.4477
0.4179
1
−0.1844
−0.1263
0.1695
0.4542
0.5143
0.4865
1
−0.8190
−0.9333
0.7915
−0.9017
−0.9139
1
0.5858
−0.8072
0.5146
0.5347
A% (Pb)
Rp
Vp
SSA
N
H
C
WRC
CEC
OM
Δ pH
pH
Clay + Silt
Table 4
Pearson's correlation matrix relating the physical and chemical characterization parameters of organic composts with the respective Pb, Zn and Cd removal percentages.
A% (Zn)
A% (Cd)
J.Z. Lima et al.
Acknowledgements
The São Paulo Research Foundation for granting a scholarship to the
first author (process number 2015/02529-4) and for providing financial
support (process number 2014/07180-7) and the National Council for
Scientific and Technological Development (for a PhD fellowship - process number 54134/2016-3; and for a productivity in research fellowship - process number 305096/2015-0) are gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data related to this article can be found at https://
doi.org/10.1016/j.jenvman.2018.08.047.
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