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Sorption and degradation of petroleum

hydrocarbons, polycyclic aromatic hydrocarbons,
alkylphenols, bisphenol A and phthalates in
landfill leachate using sand, activated carbon and
peat filters

Yuliya Kalmykova a,*, Nashita Moona a, Ann-Margret Strömvall a,

Karin Björklund a,b
a
Department of Civil and Environmental Engineering, Chalmers University of Technology, 412 96 Gothenburg,
Sweden
b
Department of Civil Engineering, The University of British Columbia, 6250 Applied Science Lane, Vancouver, BC,
Canada V6T 1Z4

article info abstract

Article history: Landfill leachates are repeatedly found contaminated with organic pollutants, such as
Received 3 December 2013 alkylphenols (APs), phthalates and polycyclic aromatic hydrocarbons (PAHs) at levels
Received in revised form exceeding water quality standards. It has been shown that these pollutants may be present
27 February 2014 in the colloidal and truly dissolved phase in contaminated water, making particle sepa-
Accepted 7 March 2014 ration an inefficient removal method. The aim of this study was to investigate sorption and
Available online 16 March 2014 degradation of petroleum hydrocarbons (PHCs), selected APs, bisphenol A (BPA), phthalates
and PAHs from landfill leachate using sand, granulated activated carbon (GAC) and peat
Keywords: moss filters. A pilot plant was installed at an inactive landfill with mixed industrial and
Contaminated water household waste and samples were collected before and after each filter during two years.
Organic pollutants Leachate pre-treated in oil separator and sedimentation pond failed to meet water
Colloid quality standards in most samples and little improvement was seen after the sand filter.
Filtration These techniques are based on particle removal, whereas the analysed pollutants are
Adsorption found, to varying degrees, bound to colloids or dissolved. However, even highly hydro-
Degradation phobic compounds expected to be particle-bound, such as the PHCs and high-molecular
weight PAHs, were poorly removed in the sand filter. The APs and BPA were completely
removed by the GAC filter, while mass balance calculations indicate that 50e80% of the
investigated phenols were removed in the peat filter. Results suggest possible AP degra-
dation in peat filters. No evidence of phthalate degradation in the landfill, pond or the
filters was found. The PHCs were completely removed in 50% and 35% of the measured
occasions in the GAC and peat filters, respectively. The opposite trend was seen for
removal of PAHs in GAC (50%) and peat (63%). Oxygenated PAHs with high toxicity were
found in the leachates but not in the pond sediment. These compounds are likely formed in
the pond water, which is alarming because sedimentation ponds are commonly used
treatment techniques. The oxy-PAHs were effectively removed in the GAC, and especially

* Corresponding author. Tel.: þ46 (0)31 772 2162; fax: þ46 (0)31 772 2128.
E-mail address: yuliya@[Link] (Y. Kalmykova).
[Link]
0043-1354/ª 2014 Elsevier Ltd. Open access under CC BY-NC-ND license.
 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7 247

the peat filter. It was hypothesized that dissolved compounds would adsorb equally well to
the peat and GAC filters. This was not completely supported as the GAC filter was in
general more efficient than peat.
ª 2014 Elsevier Ltd. Open access under CC BY-NC-ND license.

assume that adsorption filters will be suitable treatment for

1. Introduction dissolved and colloidal OPs in leachate and stormwater, as
they have been proven successful in previous research on
Removal of petroleum hydrocarbons (PHCs), selected alkyl- organic contaminants in wastewater (Liu et al., 2011; Ray et al.,
phenols (APs), bisphenol A (BPA), phthalates and polycyclic 2006; Tsai et al., 2006).
aromatic hydrocarbons (PAHs) and their degradation products The criteria for selecting filter material for this study
oxygenated PAHs (oxy-PAHs) from landfill leachates are of included: adsorbent affinity for the targeted pollutants;
high importance to meet the demands in the European Water adsorption capacity; and hydraulic properties. Organic-based
Framework Directive. Alkylphenols e including 4-nonylphenol filters often show an affinity for hydrophobic OPs, along
(4-NP), 4-t-octylphenol (4-t-OP) and 4-t-butylphenol (4-t-BP) e with the possibility of biological degradation if a microbial
bisphenol A (BPA), phthalates and PAHs have previously been community is established. Studied pollutants differ in their
reported in wastewater (Aparicio et al., 2007; Sanchez-Avila polarity from the least polar PAH to polar APs; therefore ad-
et al., 2009; Ballesteros et al., 2006), urban snow (Bjorklund sorbents with both polar and nonpolar surfaces are suitable.
et al., 2011; Fries and Püttmann, 2004; Reinosdotter et al., For this study, granulated activated carbon (GAC) and
2006), runoff (Bjorklund et al., 2009; Bressy et al., 2012; Sphagnum peat moss were selected. In addition, a sand filter
Clara et al., 2010; Strömvall et al., 2007) and landfill was studied as an inorganic example and because of its
leachate (He et al., 2009; Kalmykova et al., 2013; Slack et al., frequent application in leachate and stormwater treatment.
2005). In Sweden, landfill leachate is often treated in Activated carbon is a widely available material that has been
nearby wastewater treatment plants (WWTP). However, in used for water treatment already in the 19th century
pursuit of the national proposition suggesting that 40% of the (Department of The Army 2001). It is produced by heating of
phosphorous in sludge should be recycled on arable land by coal, peat or wood at temperatures between 400 and 600  C in
2018, many WWTPs are undergoing agricultural-quality cer- the absence of oxygen. Using waste materials such as coconut
tification of sludge, which demands disconnection of landfill shells as raw material reduces the GAC price and potentially
sites from the WWTP (Swedish Water, 2013). The scientific provides an environmental benefit. In addition, GAC can be
challenge is to develop local treatment technologies with regenerated or reactivated several times and re-used in the
high efficiency to remove organic pollutants (OPs), organic filters. Due to its large surface area and non-polar surface,
matter, metals and nitrogen compounds occurring in com- GAC is efficient for adsorption of non-polar pollutants (Bansal
plex mixtures in landfill leachate (Ocampo-Perez et al., 2012; and Goyal, 2005). However, in the presence of carbon-oxygen
Plosz et al., 2010; Renou et al., 2008; Rocha et al., 2013; Wu surface groups, polar compounds and metal cations can also
et al., 2011). be adsorbed. Sphagnum peat is a low-cost adsorbent, widely
Recently, OPs were shown to be present in dissolved and available, biodegradable and a natural, renewable resource.
colloidal forms in stormwater and landfill leachate The oxygen-containing functional groups in peat, such as
(Kalmykova et al., 2013). Alkylphenols, BPA, phthalates and carboxyl, hydroxyl, and carbonyl groups, provide adsorption
PAHs, including the most hydrophobic compounds, were sites for metals and polar compounds while the nonpolar
detected in a majority of filtered samples (<0.7 mm, 12 sam- parts such as waxes and methyl groups adsorb hydrophobic
pling sites) and frequently in the colloidal phase. The study organic molecules (Kalmykova et al., 2008). Earlier studies
also showed that calculated KOW values of specific organic have shown extensive adsorption capacity of peat for heavy
pollutants were lower than theoretical values and dissolved metals (Brown et al., 2000; Kalmykova et al., 2008), oils (Cohen
organic carbon (DOC) colloids were suggested carriers of pol- et al., 1991), pesticides (Smith et al., 1978), phosphorous and
lutants in the colloidal phase. These findings suggest that the nitrogen (Brown et al., 2000).
mobility and consequently toxicity and associated risks of the The aim of this study is to investigate the removal and
compounds are potentially higher than previously believed. degradation of PHCs, selected APs, BPA, phthalates, PAHs and
Hence, efficient treatment methods for stormwater and oxy-PAHs from landfill leachate by a sand, GAC and peat moss
landfill leachates targeting OPs should be developed to pre- filters in an in-situ pilot treatment plant. The hypotheses are
vent their transport to surface waters. that:
The landfill in the current study was among the sites where
high concentrations of OPs were previously measured and
frequently found in the dissolved and colloid-bound phases 1. Conventional treatment techniques, such as oil separators
(Kalmykova et al., 2013). This explains why the current and sedimentation ponds, are not efficient in removing
leachate treatment, which is among the most commonly used colloidal and dissolved OPs. To meet water quality stan-
for landfill leachate and stormwater, consisting of an oil dards, adsorption filters should be used to further reduce
separator and a sedimentation pond, is not effective. We the concentrations of OPs in landfill leachate;
248 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7

Fig. 1 e Pilot plant facility with sand, GAC and peat filters and the leachate sampling points 1e6 (all dimensions are in [mm]).

2. Highly hydrophobic compounds, such as high molecular 2.2. The plant

weight (HMW) phthalates and PAHs, and to some extent
APs, are attached to particles hence effectively removed by The pilot plant was installed on-site at the Brudaremossen
all the tested filters; landfill, close to the leachate sedimentation pond. The plant
3. The compounds previously detected in the truly dissolved was kept inside a container (i.e. without sunlight) at ambient
phase, e.g. 4-t-BP, 4-t-pentylphenol and naphthalene, will temperature and consisted of two series of sorption columns:
adsorb well in both the peat and GAC filters, while those 1) two columns with GAC and; 2) a Sphagnum peat moss col-
found in the colloidal phase, such as low molecular weight umn followed by a GAC column (Fig. 1). A sand filter was
(LMW) PAHs and BPA, will be removed by the GAC filter installed to protect the sorption filters from high concentra-
through co-sorption with humic colloids, but not by the tions of iron precipitates and to remove large particles present
peat or sand filters. in the pond water. The leachate was pumped from the sedi-
mentation pond outlet, at the point from where it is conveyed
to the WWTP, to the sand filter (sampling point 1, Fig. 1), which
was backwashed once a week. From the sand filter, leachate
2. Material and methods
flowed by gravity at a constant 1.4 L/min rate into the parallel
GAC and peat column systems as the sand filter was raised
2.1. Study site
2 m above. Stainless steel columns and copper pipes were
used. The volume of the GAC and peat columns when filled
Leachate from the Brudaremossen landfill in Gothenburg,
was 78.5 L and 102.1 L, respectively. The contact time was 20
Sweden was chosen for this study for two reasons: i) it has
and 30 min in the carbon and peat columns with corre-
been shown to contain all the compounds in question and
sponding hydraulic loading rates of 12.8 m/h and 9 m/h,
in considerable concentrations (Kalmykova et al., 2013); ii)
respectively. The columns were kept saturated at all times,
it is situated in a forest-and-lakes area with possible
with a water mirror above the adsorbent.
emission routes to surface and ground waters, the lakes are
also used for drinking water supply. The landfill was in use
1936e1976 and contains a mixture of household and in- 2.3. Adsorbents
dustrial waste with high organic content. A previous study
of the landfill showed moderate metal and APs leachate The Sphagnum peat was obtained from a horticultural firm in
concentrations, whereas concentrations of 4-t-BP, di(2- Sweden. Properties are as follows: a decomposition degree of
ethylhexyl) phthalate (DEHP) and PAHs were higher than H 5 to 6 (von Post scale), packing density 357 kg/m3, particle
in other studied landfills (Kalmykova et al., 2013). The size 2.0e5.6 mm, organic content 80%. The Filtrasorb 400
Brudaremossen leachate has to be disconnected from the ChemvironCarbon GAC has a density of 450 kg/m3, particle
WWTP by 2015. size 0.8e1.2 mm, surface area 1050 m2/g by N2 BET, and
 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7 249

Table 1 e Phenol, phthalate and PAH concentration ranges and medians (mg/L) at the sand inlet and outlet (sampling points
1 and 2, respectively, Fig. 1), number of samples (n) and samples with concentrations above the detection limit (>d.l.),
compared with European water quality standards. Data for individual samples are found in the Table S1.
Compound Sand filter inlet n (>d.l.) Sand filter outlet n (>d.l.) Water quality standards
(sampling point 1, Fig. 1) (sampling point 2, Fig. 1) and guidelines
Range (median) Range (median) AA/MACa
4-Nonylphenol 4-NP 0.41e0.67 (0.48) 5 (5) 0.11e0.87 (0.46) 12 (12) 0.3/2.0
Nonylphenol NP1EO <0.10 5 (0) <0.10e0.17 (<0.10) 12 (1) ‒b
monoethoxylate
4-tert-Octylphenol 4-t-OP 0.28e0.49 (0.43) 5 (5) 0.21e0.5 (0.40) 12 (12) 0.1/NAc
Octylphenol OP1EO <0.10e0.05 (<0.10) 5 (2) <0.001e0.04 (0.02) 12 (7) e
monoethoxylate
4-tert-Butylphenol 4-t-BP 0.34e4.5 (1.1) 5 (5) <0.001e6.2 (0.02) 12 (7) e
4-tert-Pentylphenol 4-t-PP 0.14e0.54 (0.36) 5 (5) 0.06e0.7 (0.02) 12 (12) e
Bisphenol A BPA <0.10e0.03 (<0.10) 5 (2) <0.001e9.3 (0.03) 12 (10) e
Dimethyl phthalate DMP <0.10 5 (0) <0.10 12 (0) e
Diethyl phthalate DEP <0.05 5 (0) <0.005e0.11 (<0.005) 12 (2) ‒/‒
Di-n-butyl phthalate DnBP <0.05 5 (0) <0.005e0.15 (<0.005) 12 (1) e
Butyl benzyl phthalate BBP <0.05 5 (0) <0.005 12 (0)
Di-(2-ethylhexyl) DEHP <0.05e0.18 5 (1) <0.005e58 (0.12) 12 (7) 1.3/NA
phthalate
Di-n-octyl phthalate DnOP <0.05 5 (0) <0.005e5.6 (<0.005) 12 (1) e
Diisononyl phthalate DINP <0.05 5 (0) <0.005 12 (0) e
Diisodecyl phthalate DIDP <0.05 5 (0) <0.005e0.21 (<0.005) 12 (2) e
Naphthalene NAP <0.01 4 (0) <0.01e31 (<0.01) 12 (1) 2.4/NA
Acenaphthylene ACY <0.01e0.03 (<0.10) 4 (1) <0.01e56 (<0.01) 12 (2) e
Acenaphthene ACE <0.01 4 (0) <0.01e101 (<0.01) 12 (1) e
Fluoranthene FL <0.01e0.12 (<0.10) 4 (1) <0.01e102 (<0.01) 12 (3) 0.1/1
Phenanthrene PHE <0.01e0.04 (<0.10) 4 (1) <0.01e18 (<0.01) 12 (1) e
Anthracene ANT <0.01e0.04 (0.02) 4 (3) <0.01e41 (<0.01) 12 (2) 0.1/0.4
Fluorene FLU <0.01e0.14 (<0.10) 4 (1) <0.01e64 (<0.01) 12 (2) 0.1/1
Pyrene PYR 0.04e0.13 (0.10) 4 (4) <0.01e85 (<0.01) 12 (12) e
Benzo[a]anthracene BaA <0.01e0.06 (<0.10) 4 (1) <0.01 12 (0) e
Chrysene CHY <0.01e0.06 (<0.10) 4 (1) <0.01 12 (0) e
Benzo[b,k]fluoranthene BbkF <0.01e0.03 (0.01) 4 (2) <0.01e34 (<0.01) 12 (1) 0.03/NA
Benzo[a]pyrene BaP <0.01e0.06 (<0.10) 4 (1) <0.01 12 (0) 0.05/0.1
P
Benzo[g,h,i]perylene BPY <0.01e0.06 (<0.10) 4 (1) <0.01 12 (0) ¼ 0.002/NA
Indeno[1,2,3-cd]pyrene INP <0.01 5 (0) <0.01 12 (0)
Dibenzo[a,h]anthracene DBA <0.01 5 (0) <0.01 12 (0) e
a
AA ¼ annual average and MAC ¼ maximum allowable concentration for inland surface waters (Environmental quality standards in the field of
water policy, 2008).
b
Not available.
c
Not applicable.

organic content 86%. To begin with, sand and pebble (Råda- Samples were collected from the inlet (sampling point 2, Fig. 1)
sand, Fig. 1) were filled at the bottom of the columns in three and the outlet (sampling points 3e6, Fig. 1) of each of the four
homogeneous layers of size ranges: 10e25 mm (density columns once a week for analysis of PHCs and metals, and
1440 kg/m3), 5e10 mm (density 1440 kg/m3) and 1.2e2 mm once a month for analysis of PAHs, phenols and phthalates.
(density 1400 kg/m3). The peat and GAC adsorbents were General water quality parameters including TOC/DOC, pH,
soaked in water overnight. The resulting slurry was continu- dissolved Fe, conductivity, oxygen and alkalinity were
ously mixed and introduced to the column in small portions measured in the weekly samples. The leachate was collected
under bottom-up water flow, which ensured a homogeneous as grab samples in solvent-rinsed stainless steel buckets from
adsorbent medium. Before start-up of the plant, the columns which 1 L samples were separated into dark solvent rinsed
were conditioned for one week by a clean water rinse to obtain glass bottles, kept at þ4  C and directly sent to the commercial
a stable compaction. A metal grid was placed above the peat laboratories for chemical analysis of OPs. Water samples were
material to prevent material loss during backwash. This was also collected weekly in the sedimentation pond (sampling
not necessary for the GAC columns as the material is heavy. point 1, Fig. 1). Two sediment samples were collected from the
pond, and filter material from all four sorption columns were
2.4. Sampling and chemical analysis collected by core sampling after cessation of the facility and
draining of the columns. From the first GAC and peat columns,
The plant was run for two consecutive years between mixed samples of the upper 10 cm of the core were collected
AprileNovember (2011) and JuneeNovember (2012) and for analysis of the OP occurrence and indication of OP degra-
stopped, but left water-filled, during the winter season. dation in the columns. From all filters’ cores, mixed samples
250 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7

Fig. 2 e Total concentrations (left y-axis, mg/L, bars) of selected phenols, PAHs and phthalates in leachate before and after
each treatment step of the current full-scale facility at the Brudaremossen landfill, and detection frequencies (right y-axis, %,
points) of each compound in the total, colloidal and dissolved phases (data from Kalmykova et al., 2013). The numbers
below the x-axis denote the hydrophobicity as log KOW. The 4-t-BP and DEHP concentrations are scaled down to fit the
graph.

of the upper and lower 2 cm were dried and the organic con- in solids and water were analysed by GCeMS. Total organic
tent and dry density were determined and compared with the carbon, DOC were measured by TOC-V CPH (Shimadzu, Japan)
original material packed in the columns. following the method SS-EN 1484, UV adsorption by UV-1800
Included in the study are 16 specific PAHs, nine oxy-PAHs, (Shimadzu, Japan). Iron was analysed on samples filtered
BPA, 4-t-octyl- and 4-nonylphenols and their ethoxylates, 4-t- through 0.45 mm cellulose-acetate filters using the HACH
butyl- and 4-t-pentylphenol, eight phthalates and phthalate method 8008. Conductivity, pH and oxygen were measured
monoesters (Table 1, S1). Water samples were analysed by the with electrodes connected to a Multiliner P4 universal meter.
commercial laboratory GALAB, Germany. Samples for analysis
of phenols, PAHs and phthalates were weighted, internal
2.5. Mass balance calculations
standards were added and the samples liquideliquid extrac-
ted (LLE) three times with dichloromethane. The extracts were
To estimate mass balances of pollutants in water, it was
concentrated by rotary evaporation followed by drying
assumed that measured concentrations (sampled monthly)
through Na2SO4, evaporated to 1.0 ml by N2 and analysed by
were valid for the days preceding the sampling, up to the
GC-MSD. For phthalate monoester analysis, samples were
previous sampling occasion. The cumulative time between
acidified and internal standard added; extracted with organic
sample occasions was multiplied by the average flow rate and
solvent; evaporated; derivatized using MSTFA followed by GC-
the measured concentration to get the pollutant mass. Mass
MSD (EI) analysis in SIM mode. All pollutants in sediment and
balances were calculated for pollutants with at least six inlet
column materials and oxy-PAHs in water were analysed by
concentrations above detection limit. An exception was made
commercial laboratory ALS, Sweden. The following extraction
for the sand filter where five values were used for calculations.
and analytical methods were used for solids: dry substance
analysed according to SS028113/1or DIN 38414-S22; PAHs were
solvent extracted using acetone:hexane:cyclohexane (1:2:2)
and analysed by GCeMS; oil index and alkane fractions 3. Results and discussion
(C10eC40) were solvent extracted with acetone/hexane, florisil
clean-up according to CSN EN 14039 and analysed by GC-FID; 3.1. Organic pollutants in the landfill leachate
OPs/OPEOs and NPs/NPEOs were analysed using GCeMS,
phthalates were solvent extracted with n-hexane on homo- Water characteristics such as pH, temperature (Co), oxygen
genised samples, then analysed using GCeMS; oxy-PAHs both content (mg/L), redox potential (mV), conductivity (mS/cm),
 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7 251

Fig. 3 e Removal (% of inlet mass) of compounds using sand, peat and GAC filters. Compound hydrophobicity (KOW)
increases to the right on the x-axis. For the sand filter, negative removal was estimated for BPA, 4-NP and C12eC16 while for
DEHP no estimation was made due to too few samples above detection limit.

colour (pt Co) and concentrations of TOC/DOC at all sampling environmental quality standards for OPs (n ¼ 12 exceeding
points 1e6, see Table S1. annual average, AA), NPs (n ¼ 10 exceeding AA) and DEHP
Fig. 2 shows that the pollutant concentrations are in the (n ¼ 2 exceeding AA) in surface waters. The European water
same order of magnitude before and after the current treat- quality standards for PAHs were exceeded in all samples
ment steps at the landfill (oil separator and sedimentation where the substances were detected (Table 1). In contrast, the
pond), which indicates inefficient treatment (data from GAC and peat filters effectively removed the pollutants far
Kalmykova et al., 2013). The pollutants were frequently below the thresholds and often below the detection limit.
detected in the dissolved phase, suggesting that colloid- Mass balance calculations of compounds in the filters
facilitated transport or transport of truly dissolved OPs cau- reveal that considerable removal of pollutants is taking place
ses the inefficient removal by the oil separator and the sedi- in the organic filters, especially in the GAC filter (Fig. 3, data for
mentation pond. other compounds were too few to calculate mass balances). It
In the sand filter inlet (Table 1) 4-NP, 4-t-PP, 4-t-BP, 4-t-OP should be noted, that the purpose of the mass balance
and PYR were detected in all samples, and in concentrations calculation is a relative comparison of different materials and
one order of magnitude higher than concentrations reported indication of their efficiency for groups of pollutants. Recog-
for leachates from Japan, except for 4-t-OP, but similar to re- nizing the uncertainty of calculation due to few values, the
ported data for Swedish landfills (Asakura et al., 2004; Herbert mass balance results should not be used for projecting treat-
et al., 2006; Kurata et al., 2008; Öman and Junestedt, 2008, see ment facilities. The removal of 4-t-BP, BPA, 4-t-PP, 4-t-OP and
Table S2 for details). Concentrations of other analysed APs and OP1EO by the GAC filter has the highest certainty in the esti-
all the phthalates were generally lower than elsewhere re- mation because inlet values were consistently above and
ported concentrations. The median PHC concentration (oil outlet values below the detection limit.
index ¼ 84 mg/L) and the dominating fraction C16eC35 found in The hypothesis was that the HMW compounds, such as
the leachate (Table S1) are comparable to data from a previous DEHP, PYR and higher alkanes, would be removed well in all
Swedish screening of PHCs in leachate (Junestedt et al., 2003). filters as these compounds are found attached to particles.
Indeed, PYR removal is high in all the filters which suggests it
3.2. Overall improvement of water quality being particle-bound (Fig. 3). In addition, DEHP is the only
compound for which the peat filter shows as good removal
The sand filter was inefficient in improving the water quality efficiency as the GAC filter. The sand filter reduced the con-
to meet the environmental quality standards (Table 1). The centrations of higher alkanes considerably, which suggests
outlet concentrations repeatedly exceeded the European them being present in the particulate phase. However, peat
252 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7

colloids. However, 4-t-BP and 4-t-PP were removed to a higher

degree in GAC than peat and almost 80% of the BPA was
removed in the peat filter (Fig. 3). The results suggest that the
pollutants exist in both truly dissolved form and attached to
colloids, see Fig. 2 for guidance on pollutant partitioning. The
GAC filter will adsorb both dissolved and colloidal compounds,
whereas the humic colloids and thereto attached pollutants
are not adsorbed by the peat filter. Hence, the GAC filter shows
slightly higher removal efficiencies for these compounds.
The PAHs were completely removed in 50% and 63% of the
measured occasions in the GAC and peat filter, respectively.
Removal of PYR in the filters was dependent on the inlet
concentration, as it was completely removed when the con-
centration was in the same range as other PAHs, but was only
reduced by 30e70% when the initial concentration was
50e70% higher than other PAHs. The number of samples with
moderate PYR concentrations was however too limited to
statistically prove this relationship. Pyrene was effectively
Fig. 4 e The relative composition (%) of 2- to 5-ring PAHs in removed also by the sand filter. However, the relative
pond sediment and leachate before and after the different composition of other PAHs before and after the sand filter was
filters (sampling points 1e4 according to Fig. 1). similar, which is an indication of PAHs passing through the
sand filter without being retained or degraded (Fig. 4).

3.3. Petroleum hydrocarbons

and GAC showed lower efficiency for these pollutants. Mod-
erate removal of 4-t-PP and 4-t-OP and no removal of BPA and
About one hundred water samples, collected before and after
4-NP in the sand filter offer support to previous findings of
the filters, and two sediment samples were analysed for
their considerable presence in the dissolved phase
concentrations of PHCs (Table S1). In eluates from all filters,
(Kalmykova et al., 2013). However, 4-t-BP was efficiently
the C16eC35 alkane fraction was found in the highest con-
removed by the sand filter, despite it being previously found in
centrations, whereas the C35eC40 fraction was more rarely
the dissolved phase. The incoming high particle, DOC and Fe
detected (Fig. 5). Neither the composition nor the concentra-
concentrations may have caused it to be particulate-bound. It
tions of PHCs were highly affected by the particle removal
was also hypothesized that the compounds frequently
process in the sand filter. The PHCs were effectively sorbed
detected in the truly dissolved phase, e.g. 4-t-BP and 4-t-PP,
and completely removed in 50% and 35% of the measured
would adsorb well to both peat and GAC, while those found in
occasions in the GAC and peat filters, respectively.
the colloidal phase, e.g. LMW PAHs and BPA, would be better
When the sand filter was saturated with iron particles and
removed by the GAC filter through co-sorption with humic
in need of back wash, it was bypassed and leachate with high

Fig. 5 e The average concentration (mg/L, left y-axis) and relative percent composition (right y-axis) of alkanes before and
after different filters.
 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7 253

Fig. 6 e Alkylphenol and alkylphenol ethoxylate concentrations (ng/L) in the peat filter outlet.

particle, TOC/DOC and dissolved Fe concentrations was hydrocarbons are produced (Mao et al., 2009). No signs of PHC
directly conveyed to the GAC and peat filters. Under these degradation were detected in the leachates; if degradation had
conditions, the PHCs were less effectively adsorbed and occurred, the more LMW and water soluble C10eC12 fraction
leached out from the GAC, and especially the peat filter. As would have decreased significantly. In a degradation study of
suggested by the strong correlation (r ¼ 0.7) between the inlet PHCs in soil, the n-alkanes were found to be even more
and outlet concentrations, and by the unchanged resistant to degradation than PAHs with up to three aromatic
percentage composition of the alkane hydrocarbons rings (Mao et al., 2009).
C10eC12:C12eC16:C16eC35:C35eC40 in the inlet 14:30:55:6 and at In the pond sediments (Table S4) the mean PHCs concen-
the outlet 15:33:52:7 (Fig. 5), the PHCs were transported trations were 5400 mg/g for C16eC35 > 740 mg/g for
through the peat filter without being adsorbed. Colloid- C12eC16 > 510 mg/g for C35eC40 > 69 mg/g C10eC12. The relative
facilitated transport of PHCs through the peat filter, probably composition of C10eC12:C12eC16:C16eC35:C35eC40 was 1:11:81:8
by DOC compounds, is likely since C12eC16, C16eC35 inlet and as compared to 17:23:55:5 in the sand filter inlet. The low
outlet concentrations correlate with DOC (r ¼ 0.58e0.74, content of C10eC16 in the sediment compared to the leachates
n>d.l. ¼ 8e18). The peat surface cannot adsorb humic com- may be explained by a combination of volatilization, partition/
pounds due to the similar negative surface charge; humic and water-solubility and degradation.
fulvic acids are degradation products of peat and constantly
emitted at trace concentrations from the peat filters 3.4. Alkylphenols and alkylphenol ethoxylates
(Kalmykova et al., 2010).
The PHC composition in the GAC filter eluate 19:16:55:14 Among the alkylphenol ethoxylates (APEOs), 4-t-octylphe-
was different compared to the inlet 14:30:55:6. The shorter nolmonoethoxylate (OP1EO) was frequently detected before
chain C10eC12 PHCs, which are more water-soluble, were and after the sand filter, while 4-t-octylphenoldiethoxylate
found in higher amounts in the outlet than the inlet, indi- (OP2EO) and nonylphenol monoethoxylate (NP1EO) only once.
cating desorption, in contrast to colloidal transport from the Alkylphenol ethoxylates were not detected in the outlet of the
peat filter. The PHCs elute from the filter column in the order GAC filter while OP1EO was detected twice in the outlet of the
as if the GAC material was saturated. It is hypothesized that peat filter towards the end of the study (Fig. 6).
the GAC is temporarily saturated with Fe and DOC, hence the Alkylphenols were completely removed by the GAC filter,
most water-soluble LMW PHCs leave the filter matrix first. except for one sampling occasion. In contrast, the peat filter
Activated carbon has previously been shown to efficiently was shown to be less effective for removal of APs. In partic-
adsorb humic and fulvic acids and is used for this purpose in ular, 4-t-BP was as a rule detected in the peat filter outlet.
drinking water treatment (Kalderis et al., 2008). However, this Bisphenol A, 4-NP, 4-t-OP and 4-t-PP were generally removed
is also a weakness of the GAC filter, as high TOC/DOC con- during the first year of the study, but leached during the sec-
centrations saturate the filter and previously adsorbed pol- ond year (Fig. 6). The leaching may be due to filter saturation
lutants may eventually leach. The GAC filter showed no sign of or APEO degradation as outlet concentrations of both 4-NP and
full saturation during this study as outlet concentrations of 4-t-OP increased gradually along with their inlet concentra-
neither TOC/DOC nor PHCs increased by the end of the study. tions decreasing (Fig. 6). Alkylphenol polyethoxylates are
Petroleum hydrocarbon degradation in the environment degraded through the loss of ethoxylate groups under both
involves both physical processes, such as adsorption, disper- aerobic and anaerobic conditions (Mayer et al., 2007). Anaer-
sion, diffusion in pores, volatilisation, chemical oxidation and obic conditions appear to favour degradation of the poly-
reduction, and anaerobic and aerobic biological processes ethoxylates into alkylphenols, e.g. iso-NP, 4-t-OP, whereas
(Yang et al., 2013). Initially, different oxygenated aerobic conditions favour the formation of carboxylated
254 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7

ethoxylates (ECB, 2002). However, mass balance calculations suspected that a plastic source, e.g. bag for transporting the
of 4-NP and 4-t-OP do not reveal any excess of the compounds filter materials, is giving rise to the DINP contamination of the
in the outlet. Therefore it cannot be concluded that degraded samples.
APEOs are the source to 4-NP and 4-t-OP in the outlet and The peat filter showed slightly higher removal of phtha-
saturation of the filter may have occurred. lates than the GAC filter throughout the study. This trend may
In general, the removal efficiency in the peat filter de- be due to the compounds’ biodegradation in peat (Peterson
creases in the following order: BPA > NP > OP > 4-BP > 4-PP, and Staples, 2003). However, as the detection frequencies of
which is the order of an increasing occurrence in the colloidal phthalates were so low, no general conclusion on the filters’
phase, previously shown in Kalmykova et al. (2013). The na- removal efficiency can be drawn.
ture of the colloids is likely to be organic, i.e. humic and fulvic It has been shown that phthalates biodegrade to a large
acids, because the pollutants are completely (apart from 4-NP) extent to monoesters and phthalic acid in landfills under both
removed by the GAC filter along with the DOC. In addition, aerobic and anaerobic conditions, while abiotic degradation is
concentrations of all of the measured APs and APEOs considered negligible (Jonsson et al., 2003b). Using landfill
increased (r ¼ 0.50e0.85, n > d.l. ¼ 6e10) with increasing inlet simulation reactors, Jonsson et al. (2003a) found monoesters
and outlet DOC concentrations in the sand and peat filters, and phthalic acid at concentrations that occasionally excee-
which confirms their colloid-facilitated transport through ded the phthalate diester concentrations by several orders of
these filters. magnitude in the leachate. In the current study, the presence
Among the studied pollutants, only the APs exhibited of mono-2-ethylhexyl phthalate, mono-ethyl phthalate and
probable relationships with water characteristics other than mono-n-butyl phthalate (degradation products of DEHP, DEP
DOC in the sand and the peat filter. A comparable analysis was and DBP, respectively) was studied in a selection of samples.
not possible for the GAC filter as few values were above the All monoesters were below the detection limit (100 ng/L) in all
detection limit in the outlet. Higher 4-NP and 4-t-OP concen- samples. However, it should be noted that the samples were
trations were measured at higher pH (varied in the range not preserved by freezing as suggested for the long-term
6.5e8.1) in the outlet of the sand filter (r ¼ 0.61e0.73, storage of samples used specifically for monoester analysis,
n>d.l. ¼ 10). This could be explained by the phenols’ higher and further degradation, for example to phthalic acid, may
water-solubility at higher pH depending on the negative have occurred during sample storage.
charges caused by loss of hydrogen; NPs pKa w 5 and OPs
pKa w 10. The 4-t-OP may be attached to humic and fulvic 3.6. Polycyclic aromatic hydrocarbons and oxygenated
acids, which are not attracted to the negative sand surface, PAHs
hence transported out of the filter. The NPs are more likely
partly soluble in water than attached to humic and fulvic acids More than 60 leachate samples and two sediment samples
at the prevailing pH. On the contrary, lower 4-NP, 4-t-OP and 4- were analysed for the concentrations of 16 specific PAHs
t-PP concentrations were measured in the outlet of the peat (Table S1). The relative composition of 2- to 5-ring PAHs before
filter at higher pH (r ¼ 0.54e0.73, n>d.l. ¼ 10). This may be and after the filters (Fig. 4) shows that the majority of the PAHs
explained by sterically hindrance of the phenols, but also the leaching from the GAC filter are HMW, indicating that the GAC
other organic pollutants, at a decreased pH in the peat matrix. filter is not efficient in sorbing HMW organic pollutants. On
At higher pH values, the peat macro-molecules open up, the contrary, the more LMW PAHs were dominant in the peat
because of the repellent forces of the negatively charges in the filter leachate. If these more water soluble PAHs leave the peat
molecules, acting as traps for larger molecules. The results in column, it may be an indication of filter saturation. This is
this study confirm this theory as the more HMW organic supported by theoretical considerations; according to the
pollutants appear to be more effectively sorbed in the peat distribution and partition theory, the LMW PAHs should be
column than in the GAC. The simultaneous increase of the released first if the filter material it saturated. The leaching
colour value and the AP concentrations in the peat filter outlet pattern of the PAHs from the GAC and the peat column could
may be an indication of colloid-facilitated transport as not be explained by colloidal transport because then there
colloidal iron and humus content are measured by colour should have been a higher colloidal transport of the HMWs in
indication (r ¼ 0.60e0.79, n>d.l. ¼ 6e10). the GAC than in the peat.
The peat column is rich in humic acids, which may
3.5. Phthalates enhance the PAH degradation rate (Smith et al., 2009). How-
ever, no signs of PAH degradation could be found in the peat
Phthalates were only sporadically detected at the sand filter column because if degradation had occurred, the most volatile
inlet and at the outlet of all filters, see Table S1. Most con- PAHs would degrade first, causing a decrease in HMW/LMW
centrations were <0.5 mg/L, except for a few samples with PAH ratio (Jonsson et al., 2007; Mao et al., 2009). In the GAC
higher concentrations of DEHP, DINP and DnOP, maximum 58, column, the LMW PAHs were effectively removed. However,
8.5, and 5.6 mg/L, respectively. The detection frequency was this is more likely due to GAC’s excellent ability to adsorb
highest for DEHP at all sampling locations, whereas other volatile hydrocarbons than degradation of the PAHs.
analysed phthalates were rarely or never detected (Table 1). The main degradation route for PAHs in soil and water is
Notably, DINP was detected in several leachate samples. This microbial degradation (Baboshin and Golovleva, 2012;
phthalate was not in use during the active period of the Bamforth and Singleton, 2005). Photochemical degradation is
landfill, but have been used increasingly since the 1990s as a also an important degradation route in air (Keyte et al., 2013),
replacement for DEHP (Statistics for Chemicals, 2013). It is water (Shemer and Linden, 2007) and surface soil (Xu et al.,
 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7 255

2013). In this study, nine oxy-PAHs with high toxicity were pollutants are effectively sorbed by GAC and the more HMW
analysed in more than 40 samples at 14 occasions (Table S3). pollutants are more effectively sorbed by peat. Oxygenated
Oxygenated PAHs were detected in four sand-filter inlet PAHs were not detected in the pond sediment or in the GAC, but
samples, and in seven sand-filter eluates, while they were were detected in surprisingly high concentrations in the peat.
below the detection limit in all the seven GAC and peat-filter The detected oxy-PAHs in peat are the same as found in pond
eluates. None of the oxy-PAHs were identified in the pond outlet, i.e. fluoren-9-one, anthracene-9,10-dione, 2-methyl
sediment samples (Table S4), indicating that these com- anthracene-9,10-dione and 4H-cyclopenta[def]phenanthrene-
pounds, with relatively high water-solubility, are transported 4-one. These results indicate that the water soluble and highly
in the water phase from the sedimentation pond. The com- toxic oxy-PAHs may be effectively sorbed in the peat column
pounds are likely formed under the prevailing aerobic and but not in the GAC. For 4-t-OP and its mono-, di- and tri-
sunlight conditions with high nitrogen (Jacobs et al., 2008) and ethoxylates, GAC contained twice as high concentrations as
iron oxide concentrations (Jonsson et al., 2007) in the sedi- peat, but for 4-NP and its mono-, di- and tri-ethoxylates the
mentation pond. The hydroxyl radical (HO) could degrade the concentrations were similar in both filters.
PAHs and may be generated by photochemical reactions in the
pond water, which includes photolysis of nitrate, nitrite, 3.8. Degradation and compaction of the filter materials
photo-Fenton chemistry, ligand-to-metal charge-transfer re-
actions or direct photolysis of coloured dissolved organic From the measurements of organic content (LOI) and dry
matter (Jacobs et al., 2008; Vaughan and Blough, 1998). In the density of the GAC and peat, before and after use in the col-
oxidation processes, a wide variety of PAH transformation umns, some small sign of degradation of the peat and carbon
products are formed, including oxygenated and hydroxylated was identified. Peat’s LOI value showed very little change,
PAHs, as well as ring-cleavage products such as aldehydes and whereas GAC from first filter showed increase in LOI value.
carboxylic acids (Bamforth and Singleton, 2005; Lundstedt This is because GAC from first filter was covered with
et al., 2007). Of these, the oxy-PAHs are of highest interest to precipitated iron oxides/hydroxides which protected the GAC
study because they are persistent, highly toxic to both human from combustion during the LOI determination, resulting in
and the environment, and are more water soluble than their lower values of organic content than expected. The Fe pre-
corresponding PAHs (Lundstedt et al., 2007). Oxygenated PAHs cipitation will cause problems when regenerating GAC filters
have shown a widespread occurrence in the environment but used in full-scale.
has previously not been analysed in landfill leachates. After the 2-year study, the GAC and peat filters showed
The oxy-PAHs detected in sedimentation pond outlet water compaction of around 10% and 20%, respectively, measured
and sand-filter eluate samples (Table S3) included fluoren-9- by the subsidence of the filter materials’ surfaces of the total
one, a degradation product of 9H-fluorene; anthracene-9,10- column length including sand.
dione degraded from anthracene; 2-methylanthracene-9,10-
dione, a product of methyl anthracene; and 4H-cyclopenta
[def]phenanthrene-4-one from pyrene. The calculated ratios 4. Conclusions
of oxy-PAH9/PAH16 in untreated leachate are similar to ratios
reported for groundwater samples (see Table S3). The lower There is evidence that conventional leachate treatment
ratio of the oxy-PAHs after the sand filter indicates that they methods such as oil separators and sedimentation ponds are
are not formed during sunlight exposure and aeration in the not effective in removing OPs, as detected pollutant concen-
pilot facility, but more likely in the sedimentation pond as trations were generally in the same order of magnitude before
suggested above; otherwise the oxy-PAH concentrations and after these treatment options (hypothesis 1). It is likely that
should have been slightly higher after the sand filter than in OPs are transported through the facility as truly dissolved and/
the pond water. or colloid-bound. Therefore, a different or complementary
treatment system efficient for dissolved and colloidal pollut-
3.7. Organic pollutants in the filter materials ants has to be found. Removal of PHCs, 16 specific PAHs, oxy-
PAHs, BPA, 4-t-OP and 4-NP and their ethoxylates, 4-t-BP and
A majority of the about 50 compounds analysed in the filter 4-t-PP, eight phthalates and monoesters was studied in sand,
materials were detected (Table S4). Total PHCs were found at GAC and peat filters. The main findings are the following:
the highest concentrations of all the analysed compound The removal efficiency of the sand filter is not satisfactory
groups in both GAC and peat; the C16eC35 alkanes was the to meet water quality standards. However, sand filter is a
dominating fraction and the highest total PHC concentration necessary pre-treatment of precipitated iron as saturation of
of 300 mg/kgDS was found in peat (Table S4). The PHC the filter material led to lower removal efficiencies for PAHs
composition in the peat filter is comparable to the composi- and PHCs in both peat and GAC filters.
tion in the pond sediment, indicating that the peat filter may Hypothesis 2 (equal removal of particle-bound pollutants
also act as a trap for iron particles. in all tested filters) appear to be only partly true for the most
The GAC contained 12 mg/kgDS of total PAHs (Table S4), hydrophobic compounds; PYR and DEHP are removed to a
which is 24 times higher than in the peat and in the same order similar degree by all filters, whereas the removal efficiency of
as concentrations in the pond sediment. The HMW phthalate the higher alkanes is lower for the peat and GAC filters. In
DEHP was 12 mg/kgDS in peat, which is seven times higher general, PHCs were the most difficult compounds to remove,
than in the GAC column. The trend seen for PAHs and DEHP is possibly because of colloid-facilitated transport from the peat
also seen for PHCs; the more volatile and water soluble filter and desorption from the GAC filter.
256 w a t e r r e s e a r c h 5 6 ( 2 0 1 4 ) 2 4 6 e2 5 7

Compounds previously detected in the truly dissolved and phthalate, nonylphenol, nonylphenol ethoxylates and
colloidal phases (DEHP, 4-t-PP, BPA and 4-NP among others) polychlorinated biphenyls in sludge from wastewater
are effectively removed by peat and GAC filters, but not by treatment plants. Anal. Chim. Acta 584 (2), 455e461.
Asakura, H., Matsuto, T., Tanaka, N., 2004. Behavior of endocrine-
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Alkylphenol degradation in peat filters was suggested. No
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combination of filters with different materials is the best so- organic pollutant flows in urban stormwater: development
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Bressy, A., Gromaire, M.C., Lorgeoux, C., Saad, M., Leroy, F.,
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