349

A publication of

CHEMICAL ENGINEERING TRANSACTIONS

VOL. 94, 2022 The Italian Association
of Chemical Engineering
Online at www.cetjournal.it

Guest Editors: Petar S. Varbanov, Yee Van Fan, Jiří J. Klemeš, Sandro Nižetić
Copyright © 2022, AIDIC Servizi S.r.l.
DOI: 10.3303/CET2294058
ISBN 978-88-95608-93-8; ISSN 2283-9216

Research on Potential Application of a New Fertilizer based

on Natural Sorbents for Toxic Soils
Olga Petrova, Gulzhan Daumova*, Zhanat Idrisheva, Assiya Mashekenova, Makpal
Kaissina
D. Serikbayev East Kazakhstan Technical university, 19, Serikbayev str., 070000, Ust-Kamenogorsk, Kazakhstan
GDaumova@ektu.kz

The article considers the study on potential application of fertilizer containing natural sorbents from Kazakhstan
deposits in order to develop a new organomineral fertilizer from household waste water and sorption materials.
There was the study on the possibility for the developed organomineral fertilizers to influence heavy metals input
into plant products, including those ones on polluted soil. There was the research on heavy metals input into
soil with meltwater on urban territory plots close to metallurgic enterprises in order to apply the proposed new
fertilizer. The following factors were defined: the required area of the plots, their service life period, produced
fertilizers application load, economically reasonable distance for transporting fertilizers. The work demonstrates
test results related to studying influence of new fertilizer types on Amoria creeping clover (Trifolium repens)
feeding crop capacity, accumulation of heavy metals in soil and plants. Content of heavy metals was defined in
plant products grown with new fertilizers application and it was proved that the proposed fertilizers were safe.
Heavy metals content in plants decreases on 2.3 - 10.2 % of heavy metals content in soil if there is fertilizer
based on shungite. Shungite-based fertilizer provides better results in copper and zinc than bentonite-clay based
fertilizer (from 0.6 to 6 % of heavy metals content in soil). But bentonite-clay based fertilizer provides better
results in cadmium and lead (0.4 - 1.9 %).

1. Introduction
One of environmental problems in big cities is utilization of domestic wastewater sludge. As a rule, after
mechanical mud is dewatered under natural conditions, sludge is stored on the territory of waste treatment
facilities at sludge draining beds or temporary storage areas and it is not further utilized. The issues of treatment
and utilization of domestic wastewater sludge are relevant for all big water service companies and represent a
serious problem. Basic existing methods of utilization are burning, dumping and using as a fertilizer. When
research results conducted in our country and abroad were analyzed, it was found that most process flows for
waste water treatment are based on the method of biological purification in aerotanks. However, this method
doesn’t provide the required efficiency of pollutant removal. As urban waste water sludge is mass with high
content of organic compounds, the main direction for its utilization is its use as a fertilizer.
When urban wastewater which is the mixture of household waste water of residential districts, domestic and
surface water flows from industrial enterprises is treated, utilization of formed sludge is a hardly-solved problem
(Tan et al., 2021), because in this case sludge contains toxic components (Santos et al., 2021). The researchers
engaged in the problem of domestic wastewater sludge utilization and development of unconventional fertilizer
types on its base (Kominko et al., 2017), distinguish a range of problems such as high hazard class due to heavy
metals content in concentrations exceeding MAC, and consequently, limited use of such fertilizers in agriculture
(Delibacak et al., 2020).
Heavy metals behaviour in soil is defined by its composition and properties. Depending on certain conditions,
heavy metals ions in soil solution can fix on the surface of different soil components and this will define their
further behaviour in soil. Such microelements as boron, cobalt, copper, manganese, molybdenum, selenium,
zinc are necessary for plants growth. However, if metals concentration in soil is high, they can be toxic for plants
and thus decrease crop yield. Metals that are not necessary can be toxic for plants and decrease crop yield.

Paper Received: 06 April 2022; Revised: 29 June 2022; Accepted: 30 June 2022
Please cite this article as: Petrova O., Daumova G., Idrisheva Z., Mashekenova A., Kaissina M., 2022, Research on Potential Application of a
New Fertilizer based on Natural Sorbents for Toxic Soils, Chemical Engineering Transactions, 94, 349-354 DOI:10.3303/CET2294058
350

Metals available for plants and amenable to leaching are present in soil solution in the form of free metal ions,
complexes and chelate compounds. During absorption by plants or leaching, there is a balance between soil
solution and solid phase. This causes relatively constant metals concentration of metals in soil solution. Metals
solubility and their availability decrease as pH increases.
Metals in soil solution constantly interact with metals in soil in the form of sediments related to soil organic
matter, absorbed by clay minerals and delayed by hydroxides. Metals in soil in the form of cations that are
capable for exchange are immediately available for absorption with plants, However, numerous researches
proved that only a few metals input into soil are capable for exchange (Li et al., 2019).
Some researchers (Geng et al., 2020) analyzed origin and chemical composition of heavy metals in sediments
and consider eco-efficient extraction of heavy metals from wastewater sludge by passive sorption and active
absorption of biomass. Potential materials that can serve as an additive for developing fertilizer from waste
water sludge are natural sorbents such as zeolite (Kotoulas et al., 2019), montmorillonite bentonite clay, as well
as compositions of sorbents with different additives. The conducted studies proved that zeolite and calurea
additives to fertilizers contribute to improving plants growth and crop yield (Lestia et al., 2018). Other authors
(Ovchinnikov et al., 2021) provided researches on wastewater sorption by means of combined charging of
zeolite and activated carbon with their further use as fertilizers. Also, biochar and zeolite were added in fertilizers
and thus plants growth was improved (Kocatürk-Schumacher et al., 2018). The use of chitosan- montmorillonite
bubbles also provided fertilizers efficiency as they contain montmorillonite clay which has the best sorption
properties (Santos et al., 2015).
Ust-Kamenogorsk waste treatment facilities sludge containing heavy metals was studied. They come together
with waste to treatment facilities and then they are concentrated in sludge in the process of purification. Waste
water that goes to biological purification in aerotanks contains Fe, Cu, Zn, Mo, Cd, Pb, Pd and other elements
in concentrations from 0.0004 to 10.79 mg/dm3. The concentration of zinc, copper and lead is the highest. Metals
are in the form of ions in sediments this causes their mobility and easy distribution in the environment. It is hard
to utilize such sludge, however taking into account properties of natural aluminosilicates, it is possible to use
them as a fertilizer under conditions that mobility of heavy metals ions in sludge is decreased after their treatment
with natural sorbents.

2. Materials and methods of research

To define the degree of soil contamination, samples of snow were taken and melt water from different areas of
Ust-Kamenogorsk and beyond by wind rose was analyzed in order to identify qualitative and quantitative
indicators of heavy metals input into soils with melt water. Snow samples were taken in the end of winter period
(March-April) before the beginning of snow melting. Snow cover samples were taken to the laboratory; snow
was melted at room temperature. Then content of different components in melted water was defined with
inductively coupled mass spectrometer ICP-MS Agilent 7500cx (Agilent, 2019).
Element-by-element chemical composition and microstructure of dry and heat-treated dry extract of melted
water were studied on scanning electron microscope JEOL JSM 6000.
To develop a new organomineral fertilizer, Koksu deposit shungites (Almaty region), and Tagan deposit
bentonite clay of horizon 14 (East Kazakhstan) were studied as additives to domestic wastewater sludge.
Shungite is a cost-effective alternative for producing organomineral fertilizer due to its structure and obvious
sorption properties. As a sorbent, shungite is characterized by a range of positive characteristics: high sorption
and catalytic properties, chemical resistance, high mechanical strength, capability of absorbing different
substances of organic and non-organic compounds. Shungite of Koksu deposit is represented by two
modifications – schistous and carbonate. Koksu deposit raw materials refer to intermediate-carbon and shungite
rocks by their carbon content. Carbonate shungite differs from schistous shungite by high carbon content (4.5 -
12 %). Average chemical composition of carbonate shungite is as follows (mass. %): SiO2 –35.5; Al2O3 – 7;
Fe2O3 - 4.52; CaO – 32.0; K2O – 2.25 (Yerbolov and Daumova, 2022). The work (Aubakirova et al., 2020)
identified the best sorption properties of shungites. Also Efremov et al. (2021) proved, that shungites modified
with ferrous chloride (III) and manganese oxide (IV) are applied in the sphere of soil protection from
contamination with different pollutants, for example, toxic components of propellant. Koksu shungite reserves
enable to supply enterprises of Kazakhstan, near and far abroad with carbon raw materials of stable quality.
There is Primanrak group in Kazakhstan – Tagan, Manrak, Dinozavr deposits of bentonite clay. Bentonite clay
of Tagan deposits differs from other clays by better sorption and physical and chemical properties, and also by
montmorillonite minerals content which exceeds 90 %. Chemical composition of bentonite clays from horizon
14 is as follows (mass. %): SiO2 – 55.48; TiO2 – 0.30; Al2O3 – 19.38; Fe2O3 – 4.40; CaO – 1.98; MgO – 2.18;
K2O – 0.51; Na2O – 0.14; SO3 – 0.18 (Mamyachenkov et al., 2017). Natural sorbents are chosen as an additive
to fertilizers considering properties related to heavy metals proved by the researchers of scientific and practical
works.
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To assess products quality that were grown in contaminated soil in the presence of fertilizers with the use of
sorbents, the area located from downwind in relation to non-ferrous metallurgy enterprise was chosen. This site
is 1 km from Ust-Kamenogorsk metallurgic complex of Kazzinc LLP.
A combined sample of soil was taken preliminarily on the site. Samples were taken in accordance with GOST
17.4.4.02-2017 «Nature protection. Soils. Methods for sampling and preparation of soil for chemical,
bacteriological, helmintological analysis» (GOST, 2019). Soil samples for analysis were prepared in accordance
with ST RK ISO 11464-2012 «Soil quality. Preliminary treatment of samples for physical and chemical analysis»
(ST RK, 2012).
The plot was divided into three zones for obtaining comparative data about the quality of the grown products –
zone 1 was sowed with plants without fertilizer addition, zone 2 – produced fertilizer with the use of shungite
raw material was preliminarily input into soil; zone 3 - produced fertilizer with the use of Tagan bentonite was
preliminarily input into soil.
Amoria creeping clover (Trifolium repens) feeding crop was chosen as test-plants in order to identify pollution
of plant products with heavy metals and hazard of their further distribution in food chain. Before sowing, the
plots were cleaned from stones, weed plants, and then they were levelled. As vegetation period began grass
was seeded into wet soil of the prepared plots 0.5 cm deep, assuming that the seeding rate is 30 g of seeds/5
m2. After that seeds sprouting test plants were watered and observed. In the end of vegetation period test-plants
condition was assessed, then they were gathered, separated from roots, washed and dried.

3. Experimental part
The work covers the choice of the plot for applying the produced fertilizers, and dependence of soil loads on
heavy metals content in the produced fertilizers. When sludge is used, the period of the plot exploitation depends
on total amount of lead, copper, nickel, and cadmium input into soil. Their MAC are established so that to provide
growth and use of crops at any time in future. Taking into account MAC values (Minister of Health of the Republic
of Kazakhstan, 2021) and heavy metals content data in Ust-Kamenogorsk waste treatment facilities sludge,
working loads of these metals sludge was calculated (Table 1).

Table 1: Working load of sludge on soil by heavy metals

Metal Total MAC of metal, kg/ha Metal content in sludge mg/kg Working load of sludge, t/ha
Lead 1,120 260 4,300
Zinc 560 2,009 280
Copper 280 200 1,400
Nickel 112 240 470
Cadmium 11 24 460

It is commonly known that significant amount of heavy metals come into soil together with atmospheric
precipitation, in particular, with melted water. Besides, during winter season pollutants are accumulated and
concentrated in melted water and then they come into soil for a short time period. It should be considered when
the produced fertilizers are used on these territories, because heavy metals coming into soil with atmospheric
precipitation will influence the load and period which is allowed for fertilizers use on this plot.
As cost-effective distance for transporting of the produced fertilizers is 50 km, it should be considered that soils
close to Ust-Kamenogorsk are under considerable technogenic influence for a long time. It should be noted that
big non-ferrous-metallurgy enterprises are concentrated on the territory of Ust-Kamenogorsk. Soils of forests
and agricultural fields that are close to mining and metallurgy enterprises activities, and populated areas are
contaminated with heavy metals which continue coming into soils via atmosphere and hydrosphere.
The concentration of pollutants is up to 15 mg/dm3 on the plots close to industrial enterprises and highways
(Table 2).

Table 2: Elements content in melted water from different plots

Sample Fe, mg/dm3 Cu, mg/dm3 Zn, mg/dm3 Pb, mg/dm3 Cd, mg/dm3
1 18.99 2.894 79 1.80 2.08
2 24.17 2.459 239 1.98 1.32
3 6.36 4.395 489 1.39 10.32
4 6.01 14.261 11,780 60.49 502.10
5 4.24 24.140 15,000 349.60 561.00
6 37.71 8.889 1,342 83.76 48.57
352

Heavy metals in melted water are not only in solution, but also in solid particles composition. Electron
microscopic study of dry and heat-treated solid extract of melted water (Figure 1) show that there are heavy
metals (Zn, Pb, Cd, Cu). It should be noted that they come with atmospheric precipitation. So the use of the new
fertilizer is relevant for decreasing toxicity, load on soil and for plot service life extension.

Figure 1: Element composition of melted water dry extract

The quality of products grown on contaminated soil were assessed in the presence of fertilizers with the use of
natural sorbents. Figure 2 shows prepared soil of the test plot with and without fertilizers from shungite and
bentonite clay.

а – soil without fertilizer, b – soil with fertilizer based on shungite, c – soil with fertilizer based on bentonite clay

Figure 2: Prepared soil of the test plot

The results of observations over sprouts of test-plants are provided in Table 3.

Table 3: Heavy metals content in soil and plants

Sample Metal content
Cu Zn Cd Pb
Without fertilizer
Content in soil, mg/kg 12.32 41.82 0.82 21.15
MACs in soil, mg/kg (Minister of Health of the
Republic of Kazakhstan, 2021) 33 55 0.5 32
MACs excess, times 0.37 0.76 1.63 0.66
Content in plants, mg/kg 2.25 3.26 0.10 1.53
 353

Table 3 (continuation): Heavy metals content in soil and plants

Sample Metal content
Cu Zn Cd Pb
Without fertilizer
MACp in plants, mg/kg (Chief State Sanitary
Doctor of the USSR, 1986) 0.1 10 50 0.5
MACp excess, times 0.22 0.07 0.99 3.05
% of content in soil 18.22 7.79 12.12 7.21
With fertilizer based on bentonite clay
Content in soil, mg/kg 13.81 43.40 0.90 23.82
MACs excess, times 0.42 0.79 1.80 0.74
Content in plants, mg/kg 1.93 2.44 0.07 0.84
MACp excess, times 0.19 0.05 0.71 1.67
% of content in soil 13.99 5.61 7.91 3.51
With fertilizer based on shungite
Content in soil, mg/kg 20.42 51.34 1.00 29.22
MACs excess, times 0.62 0.93 2.00 0.91
Content in plants, mg/kg 1.63 2.60 0.10 1.14
MACp excess, times 0.16 0.05 0.98 2.28
% of content in soil 7.99 5.06 9.81 3.90

4. Results and discussion

The obtained data provided in Table 3 shows shungite efficiency that is contained in fertilizer made of domestic
wastewater sludge. So heavy metals content in plants decreases on 2.3 - 10.2 % of heavy metals content in soil
if there is fertilizer based on shungite. Shungite-based fertilizer provides better results in copper and zinc than
bentonite-clay based fertilizer (from 0.6 to 6 % of heavy metals content in soil). But bentonite-clay based fertilizer
provides better results in cadmium and lead (0.4 - 1.9 %).
The research showed that Koksu shungite can be used for expansion of resource base for producing
organomineral fertilizers made of domestic waste water sludge. Lower concentrates of heavy metals in plants
can be achieved even on contaminated soils (1.2 - 2.3 times less than heavy metals content in soils). The
obtained results can serve as the basis for the following conclusion: it’s possible to use contaminated soils for
recultivation in case shungite-based and bentonite clay-based fertilizers are applied. Thus, natural sorbents
adsorb and neutralize potentially hazardous chemical compounds.

5. Conclusions
The peculiarities of the produced fertilizers use on soils contaminated with heavy metals were considered.
The data obtained from electron microscopic study of dry and heat-treated solid extract of melted water enabled
to identify such hazardous elements as copper, zinc, cadmium, lead and others. Besides pollutants
concentration achieves up to 15 mg/dm3 on the plot close to industrial enterprises and highways.
The work comprises the research on the possibility to use organomineral fertilizers based on waste water sludge
and natural sorbents on the soils contaminated with toxic metals.
The produced organomineral fertilizer can be effectively used on contaminated soils for recultivation due to high
sorption properties of Koksu shungite. It will enable to decrease heavy metals content in plant products 1.2 - 2.3
times of heavy metals content in soils. Also according to the obtained test results we can recommend Tagan
deposit bentonite clay from horizon 14 as an additive to wastewater sludge.
Amoria creeping clover (Trifolium repens) feeding crop enabled to identify pollution of plant products with heavy
metals and hazard of their further distribution in food chain.
The conclusions made and recommendations can be used at enterprises engaged in treatment of urban waste
water. They also can be widely used in other spheres where there is a problem of fluid and solid media
contamination with heavy metals. The developed method of sludge treatment will enable to solve the problem
of their utilization thus providing environmental safety.

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