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Remediation of Contaminated Soil Using S
Remediation of Contaminated Soil Using S
Fig. 4a: TPH concentrations. Batch 1, ditch A, B, and C, showing expo- Fig. 4b" TPH concentrations. Batch 2, ditch A, B, and C
nential decaying curve
Fig. 4c: TPH concentrations. Batch 3, ditch A, B, and C Fig. 4d: TPH concentrations. Batch 4, ditch A, B, and C
surfactant = 90 kg of surfactant, for ditches A and B. As but the function is not linear. Data were adjusted to an ex-
every surfactant solution is employed three times, it can be ponential curve, giving the following equation:
assumed that every batch consumes 30 kg of surfactant. For
ditch C, the amount of employed water is 24.8 tons, giving Removal efficiency = 0.4305 exp (0.05*removal), R2 = 0.8565 (3)
a total of 123 kg and 123/4 kg per batch process. Defining a
new removal efficiency as the amount (in grams) of TPH This means that with the washing of soils with low TPH
removed per g of employed surfactant, values between 7.88 concentrations by means of a 0.5% surfactant solution, low
and 55.45 mg TPH/mg surfactant can be achieved, as ob- percent removals are obtained, besides with very low re-
moval efficiencies, therefore wasting a lot of surfactant.
served in Table 4. Note that, in general, the higher the initial
TPH soil concentration, the higher the removal efficiency as It is noteworthy that the initial soil TPH concentration af-
g TPH/g surfactant. fects the whole washing process. Because of that, some val-
ues from Table 3 were re-arranged in Table 4, according to
Fig. 5 shows the relationship between that removal efficiency
the initial soil TPH concentration. Three blocks were con-
(g TPH/g surfactant), and the percent removal.
sidered. The first one shows the experiences within a high
It is remarkable that the higher the percent removal, the concentration range (12,000-18,000 mg/kg). Runs 1A, 4C,
higher the amount in g of TPH removed by g of surfactant, 3B, and 1B were included. They had an average initial con-
centration of 14,379, an average percent removal of 89.35%,
and a removal efficiency of 44 g TPH/g surfactant. The sec-
ond block considers the moderate concentration range
(8,000-11,000 mg/kg), runs 3C, 2B, 2A, and 3A. As noted,
they had an initial soil TPH concentration of 9,346, an av-
erage percent removal of 83.6%, and an average removal
efficiency of 28.62 g TPH/g surfactant. At the end, the block
of low range concentrations (3,000-5,000 mg/kg) includes
runs 2C, 1C, 4B, and 4A. They had an average initial con-
centration of 3,804 mg/kg, an average percent removal of
60%, and average removal efficiency of 11.63 g TPH/g sur-
factant. This means that using a 0.5% surfactant solution
for washing low TPH concentration soils, losses in removal
efficiency of 16 and 32 mg TPH/g surfactant are obtained, if
compared with the moderate TPH concentration and high
TPH concentration soils, respectively. These figures suggest
the future use of surfactant solutions with lower concentra-
Fig. 5: Removal efficiency as a function of TPH removal tions, appropriated for the TPH amount to remove.
Table 4: Analysis of the washing of soils as a function of the soil TPH-concentration range
Table 5: PAH concentrations in a composed sample of soil before and after soil washing process
Table 5 shows the PAH concentrations in a composed sam- A very rough calculation of washing soil process costs, in-
ple of soil, before and after the soil washing process. Carci- cluding labor, building materials, pumping and tubing, ditch
nogenic PAHs are highlighted in italics. In addition, the per- construction, storage tanks, and surfactant costs, among
cent removals, and required cleaning levels suggested by the others, gives a total cost of $140/m 3 or $67/kg TPH removed.
health risk assessment (PROFEPA 2000), are included for Lowe et at. (1999) report cost estimations for flushing tech-
comparison purposes. As noted, from the 16 PAH consid- nologies in the following ranges: the minimum and maxi-
ered by USEPA, 14 were found in the soil under treatment. mum are between 84 and $774/m 3. Finally, if the volume of
Only acenaphthylene, and benzo(k)fluoranthene were not NAPL removed is the target parameter, costs between 6 and
detected. The PAH which appeared in higher concentrations $63/L are typical. As noted, the costs involved in the wash-
were pyrene (9.88 mg/kg), naphthalene, and benzo(a)an- ing process are on the range of the typical costs for in-situ
thracene, both with 6.69 mg/kg. PAH removals due to the flushing methodologies.
soil washing process were in the range of 47.8 to 100%.
The case of fluoranthene is quite unusual, since an increase 2.2 Biopile development
of 33% was observed due to the washing process. This fact
could be related with soil heterogeneities. The PAH removed Soil to be treated by means of a biopile was characterized
less from soils was chrysene (47.8%), but no required clean- in terms of its bacterial count. As noted in Table 6, the
ing level is suggested for this aromatic hydrocarbon. On the amount of heterotrophs found in that soil, i.e. 1.8 x 108
other hand, naphthalene, benzo(g,h,i)perylene, fluorene, di- UFC/g soil, is quite high. Regarding the specific hydrocar-
benzo(a,h)anthracene, indene(1,2,3-cd)pyrene, and acenaph- bon degraders, it was found that bacteria with the capabil-
thene were removed to 100%. ity of degrading oil, diesel, and crude oil were detected in the
same soil, in amounts of 5.6 x 10 s, 5.4 x 108, and 1.0 x 10 s,
There are only two PAHs out of the required cleaning level. respectively (see Table 6). Fahnestock (1998) considers that
Benzo(a)anthracene should be in a concentration equal to 1 x 103 UFC/g soil of heterotrophic bacteria are enough for
or less than 0.55 mg/kg, and it was found in a concentration correct biopile function.
value of 0.57 mg/kg (1.036 times the goal value). Benzo(a)-
pyrene had a final concentration of 0.56 mg/kg, 10.37 times Table 6: Soil bacterial count (heterotrophs and degraders)
the goal value (0.054 mg/kg). Finally, a total amount of
PAHs around 50.5 mg/kg was found before the washing
process. At the end of the process, only 6.52 mg/kg re-
mained. This means an average PAH removal of 87.1%.
Very few works have reported the PAH suggested by USEPA
removal efficiencies.
In the pristine soil, only gram-positive bacteria were identified the 16 PAHs considered by USEPA were found in the com-
(Table 7). Three genera were detected specifically: Bacillus, posed sample. This means 100% efficiency in PAH removals.
Micrococcus, and Turicela. The species recognized were B. It has been reported that PAH with three aromatic rings are
brevis, B. licheniformis, M, luteus, M. sedentarius, and T. easily bio-degraded (Eriksson et al. 2000). Guerin (2000) also
otitidis. Contaminated soil showed the presence of three gen- found that the bioremediation of PAH contaminated soils is
era and species, all gram-positive too. Bacteria were Staphylo- affected by the number of aromatic rings. In a process lasting
coccus schleiferi, Micrococcus sedentarius, and Corynebacte- 224 days, approximately 90% of the 4-ring PAH, and 70% of
rium renale. There is no explanation for the presence of only the 5- and 6-ring PAH were reported as biodegraded. As shown
gram-positive bacteria. Genera found in hydrocarbon-contami- in Table 5, except pyrene (4 rings), all the PAHs present in the
nated soils by other researchers are Xanthomonas sp., Bacil- composed sample had 2 and 3 rings. The number of rings in a
lus sp., Hyphomicrobiu sp. (Li et aL 2000), Sphingornonas PAH has an effect on the compound physico-chemical prop-
pacimobillis, Sphingobacterium multivorum (Jorgensen et al. erties. As an example, PAH water solubilities are highly af-
2000), Stenotrophomonas maltophilia (Boochnan et al. 1998), fected by the number of rings in the PAH. While phenathrene,
and Rhodococcus sp. (Sharma and Pant 2000), among others. naphthalene, and fluorene have water solubilities of 1.1, 31,
Besides, some microorganisms have been reported because of and 1.9 mg/l, respectively; pyrene has a water solubility value
their capability of producing biosurfactants. Among the mi- of 0.13 mg/l (Eriksson et al. 2000). This parameter is closely
croorganisms reported for that feature are some species of related with availability and biodegradation issues.
Pseudomonas, Corynebacterium, and Bacillus (two of them Seklemova et al. (2001) reported their work with three 0.6 m 3
reported in this work), as well as Arthrobacter, Mycobacte- biopiles. They were contaminated with 2,000, 4,000, and 6,000
rium, Rhodococcus, Candida, Rhodotorula, and Streptomices, mg/kg of hydrocarbons. Biopiles were bio-stimulated with
among many others (Mulligan et al. 2001). nutrients, but not aerated (only stirred once a month). They
Biopile was operated for 66 days, during the months of Octo- observed removal efficiencies of 66, 75, and 75% after 373
ber, November and December. For these months, average tem- days of operation, respectively. Regarding the degradation
peratures are 13.1, 12.2, and 10.0~ respectively (annual rates, values of 4, 8, and 11 mg/kg/day were reached. Gogoi et
average temperature = 13.5~ (CONAGUA 2000). Fig. 6 al. (2003) worked with 500 kg cells with different treatments.
shows the biodegradation kinetic at the biopile. Though data They reported an initial TPH concentration of 44,000 mg/kg.
are scarce, the high TPH degradation rate is remarkable. Proc- Soil was amended with nutrients, and a consortium, isolated
ess started with 4,666 mg/kg of TPH, and at the end of day from hydrocarbon-contaminated soils, was inoculated. The
66, only 691 mg/kg were present on average. This means an system was aerated 1 hour a day at a rate of 100 m3/h. At the
85.2% removal, and a 60.22 mg/kg/day degradation rate. end of 365 operation days, the removal for the cell was 75%,
Biopile was no longer operated, since the goal of 2,000 mg/kg with a degradation rate of 90 mg/kg/day. Finally, Chaineau et
was clearly reached. Regarding the PAHs, Table 2 shows the al. (2003) reported experiences with a 30 m 3 biopile with an
four PAH found in a composed sample before the biopile treat- initial hydrocarbon concentration of 15,000 mg/kg. Tempera-
ment. Phenathrene (5.98 mg/kg), naphthalene (4.63 mg/kg), ture was in the range of 5-25~ during the experiments. The
fluorene (1.81 mg/kg) and pyrene (0.65 mg/kg) were found in system was amended with nutrients and mixed with straw to
the composed sample, giving a total PAH concentration of enhance textural characteristics. The pile was aerated at a 10
around 13 mg/kg. At the end of the biopile treatment, none of m3/h rate. In 500 days, they reached a removal of 50%, which
means a degradation value of 15 mg/kg/day. As observed, the
100 m 3 biopile operated successfully, reaching quite high re-
moval percentages and degradation rates, if compared with
similar biopiles reported in the literature. Note that operation
temperature was quite low (10-13.1~
A rough calculation of building and operation costs for the
100 m 3 biopile, gives a total cost of $94.2/m 3. There are no
many authors who report the field costs of bioremediation
though biopile methodologies. Fahnestok et al. (1998) re-
ported a cost analysis for biopile construction and opera-
tion. They distinguished between temporary and permanent
installations. For both, costs are an inverse function of total
volume. For temporary biopiles (as the biopile operated along
this work), costs fluctuated between 135.4 and $60.5/m 3,
for biopiles with volumes of 500 and 5,000 yd 3 (382 and
3,822 m3), respectively. As noted, the total cost reported
Fig. 6: TPH degradation kinetics in the biopile here is quite near the range mentioned.
2.3 General considerations dures, since soil washing operations can be in the order of
Clean soil was mixed and stored in piles. An evaluation of the weeks, and biopile treatment could last as much as 2-3 months.
TPH concentration (10 random samples) yielded an average
of 1,390 mg/kg (standard deviation of 283 mg/kg). Consider- 4 Recommendation
ing an initial average TPH concentration of 10,000 mg/kg, It is highly recommended to perform soil washing studies, iden-
the main features of the cleaning process were: tiffing new products, and mixtures, which could reduce costs
- Total volume of remediated soil 1,642 m 3 and assure optimum operation. Besides, it would be useful to
- Total mass of remediated soil 2,463 ton
- Total mass of initial TPH in soil 24.63 ton
determine the effect of soil washing on metals and some nutri-
- Total mass of final TPH in soil 3.42 ton ents (phosphorus, nitrogen, Na, K, Ca, Mg), as well as other
- Total mass of removed TPH 21.21 ton soil physical-chemical and microbiological characteristics.
- Average TPH removal efficiency 84%
- Total amount of employed surfactant 1.77 ton