Waste Management 63 (2017) 267–274

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

A comparison of landfill leachates based on waste composition

Chris M. Moody a,b, Timothy G. Townsend a,⇑
a
Department of Environmental Engineering Sciences, University of Florida, P.O. Box 116450, Gainesville, FL 32611-6450, USA
b
Arcadis U.S., 3109 West Dr. Martin Luther King Jr. Suite 350, Tampa, FL 33607, USA

a r t i c l e i n f o a b s t r a c t

Article history: Samples of leachate were collected from fourteen landfills in the state of Florida, United States that
Received 23 October 2015 contained primarily putrescible waste (municipal solid waste, MSW, and yard waste), MSW incinerator
Revised 15 September 2016 (MSWI) ash, or a combination of both. Assessment of leachates included trace metals, anions, and
Accepted 19 September 2016
nutrients in order to create a mass balance of total dissolved solids (TDS). As expected from previously
Available online 11 October 2016
literature, MSW leached a complex matrix of contaminants while MSWI ash leachate TDS was more than
98% metallic salts. The pH of the MSWI ash leachate samples was slightly acidic or neutral in character,
Keywords:
which is contradictory to the results commonly reported in the literature. The cause of this is hypothe-
Landfill leachate
MSWI ash
sized to be a short-circuiting of rainfall in the landfill due to low hydraulic conductivities reported in ash
MSW landfills. The difference in pH likely contributed to the findings with respect to MSWI ash-characteristic
Wastewater trace metals in leachates such as aluminum. The authors have concluded that the research findings in this
study are an indication of the differences between laboratory leachate quality studies and the conditions
encountered in the field. In addition, a characterization of organic matter using qualitative and quantita-
tive analyses determined that COD is not an accurate indicator of organic matter in leachates from
landfills with a significant fraction of MSWI ash.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction incinerator (MSWI) ash (Meima and Comans, 1997; Dijkstra

Landfill leachate is well understood to be a complex matrix of
various chemicals including organic matter, inorganic salts, organic
trace pollutants, and heavy metals, each at concentrations that
vary based on the physical (e.g., weathering), chemical (e.g., des-
orption), and microbiological (e.g., degradation of organic waste)
processes occurring inside the landfill (Kjeldsen et al., 2002).
Several factors are cited that influence leachate composition,
including the age of the landfill (Kulikowska and Klimiuk, 2008),
the depth of the waste in the landfill (Jang and Townsend, 2003),
and the local climate or season (Chu et al., 1994; Gabriela et al.,
2011; Rafizul and Alamgir, 2012). Another factor affecting leachate
quality is the composition of the waste material present in the
landfill. The bulk of the studies on landfill leachate chemical com-
position have been focused on conventional municipal solid waste
(MSW) (Ehrig, 1983; Kjeldsen et al., 2002; Kang et al., 2002; Lü
et al., 2009; Kulikowska and Klimiuk, 2008; Oman and Junestedt,
2008) and to a lesser extent construction and demolition (C&D)
debris (Weber et al., 2002; Jambeck et al., 2008). Though much
work has focused on laboratory-generated leachates from MSW
⇑ Corresponding author.
E-mail address: ttown@ufl.edu (T.G. Townsend).
et al., 2006; Inanc et al., 2007; Cappuyns and Swennen, 2008;
Quina et al., 2009; Rocca et al., 2012), leachate characterization
data from operating MSWI ash landfills are limited.
In the United States (US), an estimated 12% of MSW is
combusted in MSWI facilities. In some other countries (e.g.,
Netherlands, Denmark, Germany, France, Sweden), this percentage
is much higher (An et al., 2014). Fly ash and bottom ash generated
by US facilities are typically combined together prior to final dis-
posal in an ash monofill or a landfill co-disposing the ash with
MSW (Oehmig et al., 2015). Leachates from landfills with large
quantities of ash are expected to differ in quality compared to lea-
chates from MSW landfills. While literature describing laboratory-
generated leachate suggests that leachate produced at MSWI ash
landfills will exhibit elevated concentrations of salts, only limited
data have been published comparing leachate quality differences
among operating landfills with different levels of ash.
Understanding the characteristics of landfill leachate is essen-
tial to managing the leachate in the most efficient manner pos-
sible. The complex nature of conventional leachate generally
requires a variety of treatment technologies to target specific
contaminants (Renou et al., 2008; Pi et al., 2009; Singh et al.,
2012). In contrast, MSWI ash leachate is expected to exhibit a
less diverse constituent composition since the incineration

http://dx.doi.org/10.1016/j.wasman.2016.09.020
0956-053X/Ó 2016 Elsevier Ltd. All rights reserved.
268 C.M. Moody, T.G. Townsend / Waste Management 63 (2017) 267–274
process destroys most of the biodegradable material that would
otherwise contribute to the presence of nitrogen and organic
matter in leachate. A significant number of research experiments
have been conducted on the treatment of conventional MSW
landfill leachate (Wiszniowski et al., 2006; Renou et al., 2008);
for example, researchers routinely focus on MSW landfill lea-
chate organic matter and how properties and treatability change
as the landfill ages (Renou et al., 2008; Kawai et al., 2012). How-
ever, minimal research has been reported on the treatment of
non-conventional leachates such as those from ash monofills or
ash co-disposal facilities (Linde et al., 1995).
With the increased prevalence of the MSWI process and there-
fore MSWI ash disposal into landfills, investigating the characteris-
tics of MSWI ash leachates at operating landfills is important for
the development and refinement of effective leachate treatment
strategies. This research examines how the disposal of MSWI ash
in landfills influences leachate composition and chemistry. Lea-
chate properties – (including pH, dissolved ions, carbonate alkalin-
ity, ammonia-nitrogen, trace inorganic elements, and organic
matter) from multiple full-scale landfill sites are evaluated to
develop a better understanding of the influence of MSWI ash dis-
posal on leachate character.
2. Methods and materials
2.1. Sample collection
Landfill leachate samples were collected from July through
August of 2014 from fourteen landfills distributed throughout Flor-
ida, US. Samples were collected from five conventional landfills
receiving only MSW; three bulky debris landfills that received a
mixture of yard waste, C&D debris, and other non-putrescible
MSW; and three facilities receiving only MSWI ash. In addition,
three samples were collected from landfills that co-dispose MSWI
ash and MSW; each co-disposal landfill contained different per-
centages of ash (12%, 15%, and 70% on a mass basis). The percent-
age of total combined fly and bottom ash associated with a landfill
was provided by the landfill operator and based on waste tipping
receipts. Each of the landfills in this study that disposed of MSWI
ash disposed of the incinerator’s combined fly ash and bottom
ash streams.
In an effort to obtain a sample that best represented the landfill
leachate, samples were collected from the closest accessible sam-
pling location to the discharge pipe of the landfill; in most cases this
was a leachate collection sump or pump station located near the
perimeter of the facility. A sampling pump was used to continuously
collect leachate through a flow block. The flow block contained a YSI
Model 556 Multiparameter meter that continuously measured pH,
temperature, and conductivity. Laboratory samples were not col-
lected until these parameters stabilized. Samples were stored in a
500-mL HDPE bottle on ice until they were returned to the labora-
tory for analysis and/or preservation, which varied by the method
of analysis.
Table 1
Water quality analytical methods (Horn and Squire, 1967; EPA, 1995; APHA, 1997; ASTM, 2009).
Parameter Method number
Chemical Oxygen Demand Standard Methods: 5220D
Biochemical Oxygen Demand Standard Methods: 5210
Total Organic Carbon ASTM Method D7573
Dissolved Organic Carbon
Total Dissolved Solids Standard Methods: 2540C
Alkalinity Standard Methods: 2320B
Ammonia-nitrogen Hach Method 10031
Inorganic Anions Standard Methods: 4110
Inorganic Cations EPA Method 3010a
2.2. Leachate chemistry analysis
All methods are provided in Table 1 along with a brief descrip-
tion. The trace inorganic elements analyzed included Al, As, B, Ba,
Ca, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sb, Sr, and Zn. Leachate samples
were acid digested and analyzed using a Thermo Scientific iCAP
series 6000 ICP-AES Spectrometer. During the analysis of the trace
inorganic elements, two internal quality assurance checks were
completed. The relative difference between sample duplicates
was monitored and analyses were only accepted if this value was
less than 15%; known standards were also analyzed and results
were only accepted if the analyzed standard was within 20% of
the known value. Inorganic anions including SO4, PO4, F, Br, and
Cl were analyzed using a Dionex ICS-30000 ion chromatograph
equipped with a IonPac AG22 guard column and an AS22 analytical
column. Similar to the trace inorganic elements, relative difference
was required to be below 10%; known standards were required to
be within 10% of the known value.
American Standard Test Methods (2009) were used for the mea-
surement of total organic carbon (TOC), dissolved organic carbon
(DOC), and total dissolved solids (TDS). TOC and DOC were ana-
lyzed using a Shimadzu TOC-VCPH total organic carbon analyzer
equipped with an ASI-V auto-sampler. COD and ammonium were
measured using a DR/4000U Hach spectrophotometer. Chloride
can interfere with the measurement of COD by consuming the
chemical oxidant. During this study, mercuric sulfate was used to
reduce the interference of chloride when the concentration
exceeded 2000 ppm as recommended by the method (ASTM,
2009). Alkalinity measurements were used to estimate the concen-
tration of inorganic carbon in each sample.
The characteristics of organic matter in the samples were stud-
ied using two spectroscopic methods. Ultraviolet (UV) absorbance
was measured using a Hitachi U-2900 spectrophotometer with a 1-
cm quartz cell. This analysis measured the absorbance of wave-
lengths from 200 to 700 nm at 4 nm increments. UV absorbance
is useful in the detection of aromatic bonds between carbon atoms
in the organic matter and is commonly used as an indicator of
organic matter strength in water samples prior to coagulation
(Matilainen et al., 2010). Additionally, fluorescence excitation-
emission matrix (EEM) spectroscopy was completed using a Hita-
chi F-2500 fluorescence spectrophotometer by the excitation of
the organic matter compounds at 5-nm increments from 220 to
500 nm and measuring the emission wavelength at 5 nm incre-
ments. Fluorescence EEM has previously been used by researchers
in various applications focused on identifying organic matter
source (e.g., humic substances, fulvic acids). These methods have
been followed from previous research conducted on landfill lea-
chate (Baker and Curry, 2004; Comstock et al., 2010).
2.3. Statistical analysis of results
To assess differences between leachate samples from landfills
disposing of high amounts of MSWI ash and those not, the landfills
Description
Closed reflux, colorimetric Method
5-day incubation with oxygen monitoring
680 °C Combustion catalytic oxidation
Gravimetric Filtration and drying at 180 °C
Titration to pH of 4.5 by sulfuric acid
Salicylate Method
Chemical suppressant with eluent conductivity measurements
Acid digestion with heated reflux at 95 °C
 C.M. Moody, T.G. Townsend / Waste Management 63 (2017) 267–274
were divided into two groups based on the contribution (mass per-
centage) of ash contained in the landfill: high ash (HA) and low ash
(LA) leachate samples. The HA samples represented landfills where
the composition was greater than 50% ash, while the LA samples
contained less than 50% ash. Four samples were categorized as
HA samples (three ash monofills and one co-disposal landfill)
and ten samples (five MSW landfill samples, two co-disposal land-
fill samples, and three bulky debris landfill samples) were catego-
rized as LA samples. To identify a significant difference among
samples, a t-test was used for normally distributed samples and
a Wilcoxon rank-sum test used for non-normally distributed sam-
ples. Normality of the sample distribution was assessed using the
Shapiro-Wilk test (Zorn, 2004). These analyses were completed
using Sigma Plot (Systat Software Inc, California, USA). The results
of these analyses are shown as ‘‘P”, which represents the probabil-
ity that the hypothesis is correct. When ‘‘P” is closer to 0, there is
stronger data in support of the hypothesis.
3. Results and discussion
3.1. pH and alkalinity
Leachate pH and alkalinity were measured to gain an under-
standing of the conditions under which the leachate was formed
in the landfill. The samples collected in this study were neutral in
character with a pH ranging from 5.8 to 7.4. The pH of the HA and
LA groups ranged from 5.8 to 6.9 (mean = 6.3) and from 6.6 to 7.4
(mean = 7.1), respectively, as shown in Fig. 1. The LA samples exhib-
ited a significantly greater pH than the HA samples (P < 0.001) fall-
ing within the typically reported range for MSW landfills of 5.8–8.5
(Kjeldsen et al., 2002; Kulikowska and Klimiuk, 2008; Renou et al.,
2008; Kawai et al., 2012). Similarly, the alkalinity of the LA samples
was significantly higher than the HA samples (P = 0.02), ranging
from 1250 to 8500 mg/L (mean = 4200 mg/L) in the LA samples
and 90–950 mg/L (mean = 490 mg/L) in the HA samples (Fig. 2).
Research on leachate from operating MSWI ash landfills is lim-
ited, but laboratory leaching data on MSWI ash (typically batch or
column leaching tests) have been reported to range from 8 to 12
depending on the makeup of the ash (and the presence of air pol-
lution control residuals, such as lime) and the extent to which the
ash has weathered (Meima and Comans, 1997; Dijkstra et al., 2006;
Rendek et al., 2006; Rocca et al., 2012; Roessler et al., 2014). This
suggests that MSWI ash landfill leachate pH should be higher than
MSW leachate, but in the case of the operating landfills assessed
here, no such trend was observed. Similar observations between
laboratory-generated leachates and field-collected samples have
been reported by others (EPA, 1990; Cardoso et al., 2007). We
Fig. 1. Comparison of the pH of the HA and LA sample groups.
269
Fig. 2. Comparison of the total alkalinity of the HA and LA sample groups.
hypothesis that several factors contribute to this observation.
While rainfall short-circuiting occurs in MSW-only landfills, the
extent of this phenomenon has been shown to increase due to
the presence of MSWI ash (Johnson et al., 1998). When ash is
deposited in a landfill, it often reaches a state of relatively low
permeability, and thus much of the water is shed from the landfill
surface instead of infiltrating into and passing through the land-
filled material. Along these lines, Johnson et al. (1998) reported
that preferential flow in landfills with MSWI ash results in leachate
that is a combination of leachate produced by rainwater runoff
over the landfilled surface and leachate produced by the percola-
tion of rainwater through the ash (up to 80% of the leachate gener-
ated was found to result from runoff).
Other differences among the waste stream leachates, besides
pH, support the hypothesis that preferential flow plays a role with
respect to leachate quality. Though the initial pH of MSW (as well
as bulky debris containing organic matter such as yard trimmings)
is lower than ash, the biological decomposition of food waste and
paper products in MSW (and yard trimmings in bulky debris)
results in a highly buffered leachate because of CO2 evolution
and resulting carbonate alkalinity. The carbonate alkalinity of
MSW leachate has been reported at concentrations of up to
5000 mg/L CaCO3 (Ushikoshi et al., 2002; He et al., 2006; Singh
et al., 2012). While rainfall short-circuiting is also expected to take
place in MSW landfills, the highly buffered nature of MSW leachate
results in a leachate pH not dramatically altered by the stormwater
runoff and channeling. Ash leachate, on the other hand, is not well
buffered (Rocca et al., 2012), thus the rainwater can more notice-
ably reduce pH. The minerals that contribute to a higher pH in
laboratory experiments are not provided sufficient contact time
for dissolution as a result of stormwater; in addition, the ash pre-
sent at the surface of the landfill will carbonate more rapidly (rela-
tive to ash within the landfill) and further contribute to a lower pH
compared to fresh ash leached in the laboratory. The more soluble
minerals (e.g., chloride minerals) do contribute to the composition
of leachate originated from runoff (see Sections 3.3 and 3.4).
It is difficult to reflect on the long-term pH and alkalinity char-
acteristics of the HA leachates from the data here since each of the
HA landfills actively received waste during the study. However, as
the landfills with ash age and are eventually closed with a low per-
meability soil and/or geomembrane cap, the pH and alkalinity
characteristics may change since stormwater should have much
less influence on the generation and characteristics of leachate.
3.2. Organic matter
Three primary measurements are commonly evaluated in
wastewater to characterize organic matter strength: TOC, BOD,
270 C.M. Moody, T.G. Townsend / Waste Management 63 (2017) 267–274
and COD. TOC is a direct measurement of the organic carbon in the
sample. The results of this study found that HA samples contained
90% less TOC (10–250 mg/L, mean = 95 mg/L) in comparison to LA
samples (80–2700 mg/L, mean = 915 mg/L), an expected difference
due to the MSWI process. Most of the carbon in the waste is com-
busted in the MSWI process; the organic carbon remaining in
MSWI ash can be less than one-half of a percent (Rocca et al.,
2012). Reported values of TOC in conventional landfill leachate
range from 75 to 8800 mg/L (Renou et al., 2008; Ziyang et al.,
2009; Wu et al., 2011).
BOD is used as an indicator of the organic matter in a wastew-
ater sample subject to biological oxidation, and thus is helpful
when assessing the feasibility of biological treatment of organic
matter. BOD concentrations were found to be 90% lower in the
HA samples (30–80 mg/L, mean = 45 mg/L) compared to the LA
samples (10–950 mg/L, mean = 360 mg/L). COD is a more rapid test
than BOD, and is thus commonly used by operators to describe the
organic matter strength of landfill leachate. These results similarly
indicated lower organic matter concentrations in HA samples;
however, the difference was only by 25% between the HA samples
(310–3800 mg/L; mean = 2200 mg/L) and the LA samples (420–
6000 mg/L; mean = 2900 mg/L). Each of the three organic matter
parameters exhibited the same trend between HA and LA samples,
with the COD difference less pronounced in comparison to the TOC
and BOD analyses (discussed further in this section).
Engineers and operators often use the BOD/COD ratio to assess
the degree of organic matter stabilization in landfill leachate
(Chian and DeWalle, 1976; Kjeldsen et al., 2002; Renou et al.,
2008; Kulikowska and Klimiuk, 2008). MSW leachate has been
reported with BOD/COD ratios from 0.01 to 0.7 (Kjeldsen et al.,
2002; Renou et al., 2008), with this ratio often rapidly decreasing
in the first years of landfill operation (Kulikowska and Klimiuk,
2008). In the present study, the BOD/COD ratios of the LA samples
ranged from 0.02 to 0.25 (mean = 0.11), which indicates that the
organic matter in the LA samples was predominantly stabilized.
Similar results, though on the lower end, were observed for the
HA samples with ratios from 0.01 to 0.09 (mean = 0.04).
The chemical composition of the organic matter was character-
ized using two spectroscopic methods. Specific ultraviolet absor-
bance (SUVA) is a measure of the organic matter’s aromatic
strength, normalized to the TOC concentration, and is often used
to evaluate coagulation for the removal of organic matter
(Matilainen et al., 2010). High SUVA values (over 4) are indicative
of greater hydrophobicity and high molar mass compounds with
larger charge densities. Alternatively, low SUVA values (below 2)
indicate high hydrophilic character, low molar mass, low charge
densities, and DOC coagulation removal efficiencies lower than
Table 2
Summary of results from the fluorescence EEM analysis performed for each sample including the measured peak and corresponding substance.
Fluorophore A Fluorophore C
(Humic Acids) (Fulvic Acids)
Ash 1 X
Ash 2 X
Ash 3 X X
Co-Disposed 1 (70% MSWI ash) X X
Co-Disposed 2 (15% MSWI ash) X X
Co-Disposed 3 (12% MSWI ash) X X
MSW 1 X X
MSW 2 X X
MSW 3 X X
MSW 4 X X
MSW 5 X X
Bulky Debris 1 X
Bulky Debris 2
Bulky Debris 3 X
25% (Matilainen et al., 2010). SUVA values of the HA samples were
low, ranging from 0.7 to 2.3 (mean = 1.3), indicating that the
organic matter compounds were hydrophilic. The SUVA values of
the LA samples ranged from 1.8 to 3.7 (mean = 2.6), indicating a
mixture of hydrophobic and hydrophilic in character. The LA sam-
ples fell within the range for landfill leachates (1.9–7.4) reported
by Comstock et al. (2010), and these leachates were predominantly
hydrophobic.
Fluorescence EEM spectroscopic techniques have been used for
the identification of different types of leachate organic matter sub-
stances such as tryptophan, humic acid, and fulvic acids in the
sample (Lü et al., 2009). Comstock et al. (2010) previously studied
the fluorescence EEM results of landfill leachate and the relation to
treatment efficiency using coagulation. The results of an EEM anal-
ysis can be summarized as a collection of peaks associated with
specific pairs of excitation wavelengths and emission wavelengths,
otherwise known as fluorophores. Different substances have char-
acteristic fluorophores that allow researchers to identify the sub-
stance present in the sample. Four fluorophores are well
documented in the literature with respect to leachate organic mat-
ter (Lü et al., 2009; Huo et al., 2008; Comstock et al., 2010). The
peaks include Peak A: (Ex217–261, Em395–460), Peak C: Peak C:
(Ex300–347, Em400–461, Peak T1: (Ex270–296, Em330–380),
and Peak T2: (Ex210–247, Em329–378) (Lü et al., 2009; Huo
et al., 2008; Comstock et al., 2010). The fluorescence peaks from
the leachate samples are presented in Table 2 along with the cor-
responding fluorophore characteristics. As shown in Table 2, Peak
A was found in every leachate (except one sample that was col-
lected from a bulky-debris landfill), indicating a strong presence
of humic acids. Many leachates also exhibited Peak C, representa-
tive of fulvic acids. T1 and T2 peaks were identified in three lea-
chates with no noteworthy trends; these peaks have previously
been reported as a microbial product and were only found in a
few leachate samples that contained putrescible waste. The fluo-
rescence EEM results did not suggest any notable differences in
the types of organic matter substances present in relation to the
disposal of MSWI ash.
The EEM results provide insight to the observation that COD was
not lower in the HA samples proportional to the lower levels in BOD
and TOC. Based on the EEM results, humic and fulvic compounds
represented the primary sources of organic matter in both types of
leachate (though based on SUVA results, the properties of these
compounds differed somewhat between the HA and LA leachates).
Using an average elemental composition of these substances (Rice
and MacCarthy, 1991; Van Haandel and Van Der Lubbe, 2012), the
COD/TOC ratio of the leachates would be expected to range from
approximately 2.5 to 2.75. The LA leachate COD/TOC values
Fluorophore T1 Fluorophore T2
(Microbial Products) (Microbial Products)
X
X
X
 C.M. Moody, T.G. Townsend / Waste Management 63 (2017) 267–274
Fig. 3. COD/TOC ratios of HA and LA sample groups.
Fig. 4. Chloride concentrations of HA and LA sample groups.
(1.2–6.7, mean = 4.0) encompass this range, similar to values previ-
ously reported for MSW landfill leachates (Lo, 1996, for example,
found that as a MSW landfill aged the ratio declined from 4.1 to
2.7). The HA leachate COD/TOC values, however, ranged from 15 to
51 (mean = 27.2), much greater than the LA samples and the values
expected for organic matter dominated by humic and fulvic com-
pounds. This suggests that COD measurements for HA landfills do
not provide a reliable indication of organic matter.
While TOC measurements directly indicate organic matter, COD
measurements utilize a strong chemical oxidant, which is also cap-
able of oxidizing inorganic ions. Kylefors et al. (2003) found that
inorganic ions such as sulfide and ferric iron could be oxidized dur-
ing the COD measurement process. Chloride is known to interfere
with the COD assay at high concentrations (Horn and Squire,
1967). Kylefors et al. (2003) concluded that chloride did not play
a significant role in interfering with leachate COD measurements,
though they cautioned that their study focused on conventional
MSW leachates and not the range of chloride concentrations typi-
cal for MSWI ash leachates. Kylefors et al. (2003) worked with lea-
chates on the order of 3000 mg/L of chloride, compared to
32,500 mg/L for the HA leachates measured here. HA samples con-
tained 16 times more chloride than LA samples (Fig. 3); similarly
COD/TOC measurements were almost 7 times higher (Fig. 4). These
results suggest that the measurement of COD in the leachates from
landfills with large amounts of MSWI ash may be subject to signif-
icant interference by the presence of chloride and possibly other
reduced inorganic species (i.e., Fe, Mn, and/or S). As described in
271
Fig. 5. Comparison of the total dissolved solids of the HA and LA sample groups.
the methods, mercuric sulfate was added to the COD assays to
reduce chloride interference following standard methods, but this
does not appear to have been sufficient for the HA leachates exam-
ined. Engineers and operators should be cautious when using COD
leachate data from landfills receiving large amounts of ash for the
design of organic matter treatment technologies.
3.3. Dissolved solids
The concentrations of TDS in HA leachates were significantly
greater compared to the LA samples (see Fig. 5). The HA samples ran-
ged from 21,000 to 81,000 mg/L TDS (mean = 52,000 mg/L), com-
pared to the LA samples with a range from 2600 to 12,500 mg/L
TDS (mean = 7000 mg/L). The results of the LA sample TDS concen-
trations agree with reported values in the literature (2000–
19,000 mg/L: Li et al., 2009; Ziyang et al., 2009; Wei et al., 2012;
Singh et al., 2013). Even though rainwater short-circuiting plays a
dominant role with respect to leachate pH, the results here indicate
that sufficient interaction with rainwater at the surface layer of
MSWI ash exists to result in elevated concentrations of TDS. The
variability of the TDS concentrations among similar landfill types
was hypothesized to result from three factors: (i) variable waste
depths (Jang and Townsend, 2003), (ii) operating conditions of the
landfill (i.e., implementation of a temporary liner cap to prevent
undesired rainwater contact with waste to produce leachate), and
(iii) the previously mentioned preferential flow that will vary among
sites.
A mass balance of the TDS in each sample was performed to eval-
uate compositional differences in leachate resulting from MSWI ash.
Nitrogen, primarily in the form of ammonium, was a significant
component of the TDS in the LA samples. Overall, LA samples con-
tained a higher concentration (60–1700 mg/L, mean = 680 mg/L) of
ammonium than HA samples (20–560 mg/L, mean = 70 mg/L). LA
sample concentrations agree with reported values in the literature,
which range from 80 to 3400 mg/L, with a few cases greater than
10,000 mg/L (Renou et al., 2008; Ziyang et al., 2009; Kawai et al.,
2012; Liu et al., 2012). The ammonium concentrations were not
found to be statistically different, but the results do suggest that
the LA leachate contain higher concentrations and represented a lar-
ger fraction of leachate constituents compared to the HA samples.
High ammonia concentrations are expected to occur in MSW land-
fills as a result of nitrogen-rich food waste, but the results indicate
that some ammonia will leach from MSWI ash, possibly as a result
of the ammonia added as part of certain air pollution control tech-
nologies (e.g., selective catalytic reduction).
Fig. 6 shows the mass balance of TDS in each sample. The cate-
gories presented include organic matter, ammonium, inorganic
272 C.M. Moody, T.G. Townsend / Waste Management 63 (2017) 267–274
Fig. 6. Composition of total dissolved solids in each sample represented by five groups: bicarbonate, organic matter, ammonium, metals/metalloids, and inorganic anions.
anions, metals/metalloids, and bicarbonate. Bicarbonate was used
to represent the total inorganic carbon as the pH range of the sam-
ples indicated that the ratio of bicarbonate to carbonate was on the
order of 750. The measured TOC concentrations were used in con-
junction with the typical composition of humic acid (fraction of
carbon mass relative to mass of humic acid = 0.55) to estimate a
total organic matter mass (Rice and Maccarthy, 1991). The mass
balance in Fig. 6 represents the percentage of each mass compo-
nent relative to the dissolved solids mass. As a secondary quality
assurance check, the measurement of TDS with the gravimetric
method was compared with a summation of dissolved solids mea-
sured through individual measurements of dissolved solids; all
samples were determined to have less than 20% error.
Inorganic anions and metals/metalloids accounted for more
than 98% of the TDS in the HA samples. Conversely, the LA samples
contain a diverse, more complex mixture of components that con-
tribute to the TDS; a notable contribution to TDS resulted from
each of the five categories. Throughout all of the LA leachates,
bicarbonate represented 20–40% of the mass of the dissolved
solids. Similarly, organic matter accounted for anywhere from 5%
to 35% in the LA leachates. The fraction of TDS as metals/metalloids
in the leachate was found to be significantly higher in the HA sam-
ples (30%) in comparison to the LA samples (20%); however, the
difference between LA and HA samples is much more prominent
between the inorganic anions, which were 20% in LA samples
and 70% in HA samples. Since the mass balance was dominated
by anions in the MSWI ash leachate samples, the charge balance
was evaluated. The charge balance results indicated that the mass
balance was correct and the higher presence of multivalent cations,
such as Fe and Ca, accounted for the lower cation mass.
3.4. Trace element mobility
Concentrations of various inorganic elements for both the LA
and HA samples are shown in Table 3. This table also includes the
results of the statistical analysis (t-test or Wilcoxon rank-sum test)
identifying the sample concentrations that were significantly
different. The statistical analysis found that Ba, Ca, Fe, K, Na, and
Sr were present at higher concentrations in the HA samples in
comparison to the LA samples. Mg and Mn were found at higher
concentrations on average, though not at a statistically greater
levels. Given the significantly higher TDS in the HA leachates, as
well as the elevated presence of these elements in MSWI ash (as
compared to unburned MSW), these results were not unexpected.
Of particular interest, however, is that Al, As, Cu, Cr, Mg, Mn, Ni,
Pb, Sb, Zn were not measured at significantly greater levels in the
HA leachates compared to the LA samples. This may in part result
from the rainwater dilution effect described earlier with respect to
alkalinity and pH (the more readily soluble elements in the ash
tended to be the ones elevated in the HA samples). And perhaps
of most importance, leachable concentrations will be heavily
dependent on both the species of an element and landfill condi-
tions. The role of pH, for instance, on the leaching of heavy metals
from MSWI ash is well-established (Meima and Comans, 1997;
Dijkstra et al., 2006; Inanc et al., 2007; Cappuyns and Swennen,
2008; Quina et al., 2009; Rocca et al., 2012), and the reduced pH
conditions of the HA leachates due to rainfall short-circuiting
may cause the precipitation of many elements that may otherwise
be expected to be present in the pore water of the ash matrix.
These results illustrate the differences that may be observed
when comparing field to laboratory measurements. For instance,
Al has previously been observed to leach from MSWI ash in con-
centrations exceeding 25 ppm at (Dijkstra et al., 2006; Rocca
et al., 2012). Milne et al. (2003) concluded that under conditions
with high salt concentrations and relatively low DOM concentra-
tions, salts will compete to form complexes with DOM. Fe, which
was found to leach at a much greater concentration than Al, has
a much higher affinity for DOM than Al. Subsequently, leachate
produced by the percolation of rainwater through the waste layers
in HA facilities is more likely to contain Fe-DOM complexes and Al
in the form of Al-hydroxides. This, in combination with the rainwa-
ter dilution effect (and the resulting lower pH), could result in the
 C.M. Moody, T.G. Townsend / Waste Management 63 (2017) 267–274 273

Table 3 The findings of this study (particularly the pH, alkalinity, and
Concentrations of inorganic cations in high ash (HA) and low ash (LA) landfill sample trace metal leaching) demonstrate the importance of data from
groups with the results of the statistical analysis.
operational facilities to better understand the complex conditions
LA samples HA samples Statistical difference (P) that will influence leachate chemistry. Long-term data will be nec-
n = 10 n=4 essary to understand how these characteristics, such as pH and
Aluminum 1.44 mg/L 1.09 mg/L No (P = 0.724) alkalinity, may change after the landfill has been capped and
Arsenic 350 lg/L 70 lg/L No (P = 0.477) closed, a condition where rainfall will no longer play a dominant
Boron 6040 lg/L 1600 lg/L Yes (P = 0.034)
Barium 720 lg/L 2760 lg/L Yes (P = 0.026)
role in the generation of leachate.
Calcium 170 mg/L 4140 mg/L Yes (P = 0.006)
Chromium 180 lg/L 90 lg/L No (P = 0.229)
Copper 240 lg/L 260 lg/L No (P = 0.620) Acknowledgements
Iron 3.9 mg/L 23.3 mg/L Yes (P = 0.006)
Potassium 355 mg/L 3710 mg/L Yes (P = 0.009) The authors would like to thank the operators of the landfills
Magnesium 60 mg/L 130 mg/L No (P = 0.358)
that assisted in sample collection and provided valuable site infor-
Manganese 200 lg/L 450 lg/L No (P = 0.832)
Sodium 850 mg/L 6600 mg/L Yes (P = 0.002) mation for this work. This research was supported by the Hinkley
Nickel 160 lg/L 100 lg/L No (P = 0.138) Center for Solid and Hazardous Waste Management and the Ala-
Lead 100 lg/L 35 lg/L No (P = 0.827) chua County Public Works Department.
Antimony 90 lg/L 35 lg/L No (P = 0.775)
Strontium 1.3 mg/L 28 mg/L Yes (P = 0.006)
Zinc 100 lg/L 40 lg/L No (P = 0.776) References

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would not be similarly impacted (Meima and Comans, 1997;
Dijkstra et al., 2006; Inanc et al., 2007; Cappuyns and Swennen,
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4. Conclusions
This research was conducted to characterize leachates from
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