K Allia IDRC14 26 Aout 2014

Fate, Management and Treatment
5th International Disaster and Risk Conference IDRC 2014
‘Integrative Risk Management - The role of science, technology & practice‘ • 24-28 August 2014 • Davos • Switzerland
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of Hazardous Waste: Case of
Expired Pharmaceuticals
K. Allia, Z. Salem, L. Toumi
LSGPI-USTHB- Algiers, Algeria
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Presentation Outline
1. Objectives
2. Some issues about the damage caused by untreated
hazardous waste, their management and regulation
3. Situation of Expired pharmaceuticals In Algeria
4. Experimental work and Results
Elimination of hosphorus, Ammonium, Dyes and Recycling in civil engineering
5. Conclusion

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OBJECTIVE
This presentation refers to research project conducted under the
National Research Program (NRP) "Management and treatment of
hazardous waste" and was designed to assess the possibility of
treating and developing incineration residues (bottom ash/slag,
ash) of expired drugs.
This study allowed to understand how bottom ash/slag might
behave in the presence of three pollutants: phosphorus,
ammonium and dyes contained in some wastewater from dairies
and unit of wastewater treatment, and their possible recycling in
the civil engineering field as an additive or alternative material..

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Some issues about drugs
characteristics, the damage caused
if untreated, their management and
the current regulation

Due to their composition and properties, hazardous wastes such that expired
drugs, chemicals, present a real threat to human health, to environment and
require a set of appropriate treatments to reduce toxicity risk and
contamination, particularly for gathering pathways, transportation, treatment,
recycling and disposal.
They are considered one of the major environmental and health concerns, and
their management requires a capital interest.
Soils and sediments can sequester chemical/pharmaceuticals contaminants
which behave differently when they are present in water, air, or food and
understanding the bioavailability processes becomes essential for improving
risk assessment while recognizing priorities between different problems, and
use of resources to achieve the greatest benefit. However, this implies
contextual issues such as solubility, mass transfer, mobility and reaction, in
addition to absorption by the living organisms.
Explicitly, assess the bioavailability of contaminants is considered by many as a
way to help establish sites remediation, which involves leaving substantial
amounts of contaminants in place while remaining protective of public health
and the environment. (Luthy et al., 2003).
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If untreated, pharmaceuticals could reach the water cycle
through a variety of routes.
 When placed in landfills, such as residues from industrial
manufacturing or as unused pharmaceuticals and then infiltrate
groundwater.
 It is also possible that effluents from pharmaceutical industries
contain occasionally or permanently pharmaceutical residues and can
end up in surface water through wastewater process treatment.
In fact, physicochemical properties of such contaminants are
critical to their behavior in the water cycle and vary
considerably. They are generally organic, from the smallest and
simple substance to the largest and complex, and most drugs
are polar (water soluble), and other relatively non-polar (fat
soluble).
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In the case of sewerage, transport by rainwater as well as domestic
wastewater (combined sewer systems) networks, the peaks of transport
can occur during heavy rainfall in which a portion of the water cannot be
treated by the sewer system and the wastewater is discharged without
treatment via an overflow in surface water.
In addition, these indirect pathways to the environment are of concern
because wastewater containing pharmaceuticals can be recovered and
used for irrigation, and thus penetrate the soil and contaminate
groundwater, particularly in arid areas.
Thus an incorrect management of pharmaceutical waste can have adverse
effects on the environment and human health:
 For example, specific pharmaceutical compounds were detected in
wastewater and effluent treatment plants, rivers, lakes and groundwater.
And even though the concentrations detected are of the order of
nanograms to micrograms per liter there remains an uncertainty about
whether compounds at these levels pose a chronic threat to human or
animal health.
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In fact, it has been widely demonstrated and found that the active
compounds are present in the environment and depending on their
concentration they may have effects on fauna (case of estrogens and their
effects on fish and those of diclofenac on vultures).
Also, the effect of the active compounds on the endocrine system in
wildlife and human health has also been reported. This has led to a clear
question asked today, is this an increase or an epidemic of "environmental
diseases" which are two main groups diseases : cancer and fertility
problems.
Also, contamination of freshwater systems by industrial and home
compounds (all types) is continually increasing worldwide. Among the
major anthropogenic pollutants in large urban areas are phosphorus and
pharmaceutically active compounds from the treated wastewater.
In the case of phosphorus sources, fate and environmental impacts are
well understood, while the current knowledge of the pollution by
pharmaceuticals is lacking for effective risk management.
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Their wide range of properties means that their behavior in the water
cycle can vary considerably. However, they have some generic
properties:

They are mostly non-volatile and highly stable because, when
having been consumed, they must remain intact in order to
disperse into body and have the predicted effect.

They are also biologically active, they are designed, in low doses,
so as to have a specific effect on a given biological system.
These properties mean that the pharmaceutical may be mobile and
that is why their presence in the water cycle can be hazardous and
requires special attention.
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TREATMENT ANDWASTE MANAGEMENT
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Incineration as a practical
management of hazardous waste has
2 attributes
Permanently destroy toxic
organic compounds by
breaking their chemical
bonds and transform their
components by reducing or
eliminating their toxicity;
Reduce the amount of
hazardous waste by converting
the solid and liquid into ashes.
However to date, there are no estimates on all of these issues.
Furthermore, the legislation imposes a number of controls on the
concentrations MES, COD, BOD, nitrogen, total phosphorus,
SEC, detergents, AOX (Adsorbable Organic Halogen), phenols,
total hydrocarbons, Al, Ag, Cd, Cr VI, Cr total Cu, Fe, Hg, Pb,
Zn, nitrites and nitrates, of which most do not cover care
facilities.

Expired or unused pharmaceuticals are now incinerated in facilities
that could meet the highest environmental standards, including
treatment of smokes.
But, it seems that the drugs are not subject to discharge
authorizations. Increased use of pharmaceuticals to both humans
and animals could affect beyond immediate the consumer as they
can enter environment .
Much confusion exists about the proper way with which they
should be disposed, and many countries do not have yet the
standard protocols of medications elimination
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The material, used for our work is the bottom ash from a small
unity treating 900 tonnes/y by the following furnace
The furnace and the Flue
gas scrubber
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LEGAL AND INSTITUTIONAL FRAMEWORK
Since the Johannesburg Summit in 2002, Algeria intensified its
activities in the field of environmental protection and sustainable
development and has signed all international conventions relating
to the treatment of hazardous chemical waste.
In 1992, at the Earth Summit in Rio de Janeiro, 173 countries adopted
Agenda 21 and its chapter on "the sound management of hazardous
waste" and among them Algeria.
The existing regulation is related to industrial security, emissions and
releases to air, water and soil; the use, production and storage of
chemicals and the management and treatment of waste substances.
For the handling of chemicals, and other wastes, they are subject to
several executive orders, including those of 2001, 2003 and 2005 for
handling and transportation of hazardous chemicals.

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CURRENT SITUATION
OF EXPIRED PHARMACEUTICALS IN ALGERIA
TOTAL QUANTITY OF
SOLID WASTE
SPECIAL WASTE WASTE FROM CARE
ACTIVITIES INVOLVING
INFECTIOUS RISKS
EXPIRED
PHARMACEUTICALS
(DRCT WASTE AND TOXIC
CHEMICAL RISK)
2.55 million
tonnes/y
330,000 tonnes/y
And 2 008 500
tonnes of special
waste are stored
waiting for a disposal
solution
40 000 tonnes / year The stock is estimated
from 12 to 15 000 tonnes
and a production of
1 500 tonnes / year
(From more than 8,000
pharmacies and nearly
400 pharmaceutical
wholesalers, hospitals
and private clinics, and
each has a stock of
expired and costly drugs.)

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CURRENT SITUATION
OF EXPIRED PHARMACEUTICALS IN ALGERIA
Losses caused by this fact (expired drugs) represent 25% of
expenditure on drugs.
An agreement for the co-incineration of expired drugs was signed on
November 25, 2013 between the Lafarge Company and the Ministry
of Regional Planning and Environment .
The partnership consists on incineration at high temperature (over
1200 ° C), will be made in cement kilns equipped with combustion
gas purification located in Blida, Boumerdes, Mascara and Medea.

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EXPERIMENTAL WORK AND RESULTS
Analysis and results:
Samples of bottom ash

Physicals properties of comminuted bottom ash
100
90
80
70
60
50
40
30
20
10
Intergranular
35
30
25
20
15
10
5
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(slag)
0
0 0.2 0.4 0.6 0.8 1
%
Particles size (mm)
0
(%)
Class
Density (g.cm-3) Porosity %
Total porous volume
Apparent True +
V.P.T (cm3.g-1)
intragranular
Intergranular
1,2348 2,003 31,44 38.35 0,31

Chemical and Mineralogical Characteristics
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Absorption band
(cm-1)
Groups
Probable
identification
3452,05 - CONH Amide
2843,84 - 2915,07 C-H Alcanes
1627,40 N-H Noyau aromatique
1424,66 C-H
Alcane lié à un
aromatique
1084,93 C-N Amine
876,71 C-Cl Halogénure
Ashes
(Content
mg/l)
Cu Cd Pb As Cr
0,2173 <0,0039 0,3036 Tracs 0,21
Table 1: Identification of infrared spectra of bottom ash
(analysis by infrared spectroscopy)
Table 2: Content of metals in ash ( Atomic Absorption
Spectrometry)
Behavior of bottom ash depends on the presence of the main functional groups. The
infrared spectroscopic analysis enabled to identify them and they may be involved in fixing
on the material. These groups are: -CONH-CH,-NH,-CN, Cl-C (Table 1).
The above results (Table 2) show that the elements are a minority or trace amounts.
The X fluorescence analysis of raw and activated incinerated residues shows major
components; calcium followed by titanium, iron and chrome. The remaining heavy metals
are in trace amounts.

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EXPERIMENTAL RESULTS
PHOSPHORUS, AMMONIUM, DYES;
RECYCLING CIVIL ENGINEERING

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POLLUTANTS SOURCE OF
EFFLUENTS
INITIALS CONDITIONS RESULTS
Phosphorus Boudouaou
dairy
22.92 mg /L, 
>> standard of 2 mg /L
(0.54 mg / L << 2 mg /L)
97.5%
NH4
+ Baraki plant 19.8 mg /L  4.33 mg /L, < discharge
standard
78.5%
Dyes
1. Basic red
(Red 46)
2. Methylene
Blue (MB°
Synthetic basic red (Red 46) and methylene blue (MB), the
yields of adsorption are respectively, 62% after 270
minutes and 97.83% after 300 minutes and where the
adsorption is governed by a pseudo second-order
model for the Red 46. For the MB the application of
the intra-particle diffusion model showed that the
adsorption of MB on bottom ashes is controlled by
different phenomena (external diffusion, internal
diffusion and the fixation process of MB on the assets
adsorbent sites).

 About recycling them in the civil engineering field, as an additive or
development substitute materials, after solidification and stabilization,
the tests were satisfactory, indeed, mechanical standard tests (EN 196-1
2005) and leaching of prepared samples gave us the overall behavior of
the stabilized material.
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 The results were in good agreement from the 7th day, with a
compressive strength > 1 MPa and a COD approaching 90% and the
efficiency of stabilization process with the formation of a solid matrix
whose character of sustainability was verified and the tendency
confirmed by monitoring the evolution of the parameters until the
mortar maturation after 28 days and where all parameters keep
acceptable results.
 About the concrete, containing marble dust and incineration residues,
both are industrial wastes used in their raw state. The several variants of
concrete were investigated with assays of ℅ 0 (control concrete) ℅ 5, 10
and 15 ℅ ℅ of marble powder and 3 and 4.5 ℅ of incineration residues
have not provided significant improvement in the mechanical
resistance to compression.

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Figure 3: Views of test pieces after mold release

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CONCLUSION
• The results show that bottom ashes derived from the incineration
of expired pharmaceuticals are an efficient adsorbent for removal
of phosphates in aqueous solution and dyes in wastewater.
• About recycling them in the civil engineering field, as an additive
or development substitute materials, after solidification and
stabilization, the tests were satisfactory
• As additive and regarding to high performance concretes, based
on marble powder and ash, the mixture of marble powder and
incineration residues did not provide a significant improvement in
the mechanical resistance to compression,.
• These results are encouraging to complete the work especially in
the field of civil engineering but also reassuring as pollutants that
can infiltrate within landfills could be fixed by the bottom ashes
treated or not.

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REFERENCE:
1. Luthy, R. G. (2003). Bioavailability of contaminants in soils and sediments. Processes tools and applications. 20-46, 420 NAP
Washington, D.C. N° 0-309-08625-6 - Library of Congress.
2. Kümmerer, K. (2008), Chemosphere - Antibiotics in the aquatic environment – A review – Part I – 7, chemosphere, 11.086
3. Kümmerer, K, Hempel, K (2010), Green and Sustainable Pharmacy, DOI 10.1007/978-3-642-05199- 9_1, C, Springer
4. Derksen, A, Ter Laak T (2013). Human pharmaceuticals in the water cycle - STOWA - KWR -062.
5. Schimmelpfennig, S et al. (2012), "Seeking a compromise between pharmaceutical pollution and phosphorus load:
Management strategies for Lake Tegel, Berlin" Volume 46, Issue 13, Pages 4153–4163
6. Kümmerer, K. (2009), the presence of pharmaceuticals in the environment due to human use - present knowledge and future
challenges. Journal of Environmental Management 90, 2354-2366.
7. Voudrias, E et al. (2012). Composition and production rate of pharmaceutical and chemical waste from Xanthi General Hospital
in Greece. Waste Management 32, 1442–1452
8. Barbier M. G, (2011). Rapport sur les perturbateurs endocriniens, le temps de la précaution enregistré à la Présidence du Sénat
Français le 12 juillet sous le N° 765
9. K. Kümmerer (2009). Chemosphere - Antibiotics in the aquatic environment – A review – Part I- 75 (2009) 417–434
10. Manuel Guide - OMS (2002). PNUD / SCB OMS - Plan National de Gestion de Déchets de Soins Médicaux. Manuel Guide - OMS
Fiche N° 231.
11. Daughton CG, Ternes, TA (1999). Pharmaceuticals and personal care products in the environment: agents of subtle change?
Environ Health Perspect; 107:907–38
12. Satnam Singh, Vinit Prakash (2007). Toxic Environmental Releases from Medical Waste Incineration: A Review. Environ Monit.
Assess (2007) 132:67–81
13. RRCSE (2008) Rapport et Recommandations de l’Académie nationale de Pharmacie « Médicaments et Environnement »
Septembre.
14. Daughton C, Ruhoy I (2013). Lower-dose prescribing: minimizing “side effects” of pharmaceuticals on society and the
environment. Sci Total Environ, 443:324–37
15. Tong A, Peake BM, Braund R (2013). Disposal practices for unused medications around the world. Environ Int ; 37:292–8.
16. Convention de Bâle (1989) sur le contrôle des mouvements transfrontalier des déchets dangereux de leur élimination.
17. RGDSA (2012) Rapport pays sur la gestion des déchets solides en Algérie- Janvier 2012 (http://www.sweep-net)
18. Abdallah, H (2013). Les fours de la cimenterie « Lafarge »serviront d'incinérateurs- La Nouvelle République le 27 – 11.

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THANK YOU

Figure 3: Evolution of the adsorption yield per bottom ash on a dairy effluent from
Boudouaou Dairy.
120
100
80
60
40
20
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0
96.07 97.54
0
0 50 100 150 200
Adsorption yield (%)
Times (min)
Initial concentration [P]: 22.92 mg / L from
The Dairy Boudouaou far greater than the
standard of 2 mg / L.
The optimal conditions: concentration
[Bottom ash] = 20 g / L, pH = 7.45, T ure =
20.7 ° C, agitation speed = 200 Rpm. At
equilibrium, a yield of 97.5% is obtained
for a concentration [P] of about 0.54 mg / L
<< 2 mg / l.

Figure 4: Evolution of the adsorbed quantity by the incineration residues
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3.01
3.112
3.5
3
2.5
2
1.5
1
0.5
0
0 50 100 150 200 250 300 350
q ads (mg.g-1)
Temps (min)
Wastewater from the treatment
plant of Baraki with [NH4
+] of
(19.8 mg / L).
Yield of 78.5% is reached for an
amount adsorbed of 3.11 mg/g.
After treatment, the concentration
of [NH+] is obtained and of 4.33
4
mg / l, (value <the discharge
standard).

70%
60%
50%
40%
30%
20%
10%
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52.88%
61.34%
0%
0 50 100 150 200 250 300 350
Removal Yield
Times (min)
The adsorption yield, increases
rapidly in the first 30 min of
contact, and thus reaches 60%
after a time of 270 minutes. This
yield is reached with previously
untreated raw incineration
residues.
Figure 5: The adsorption yield of 46 RB according to the
contact time (C0 = 50 mg / L, N = 300 Rpm , pH = 9.48, Cs
= 10 g / L, T = 295.5 K)

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63.78
78.74
89.26
97.83
100
90
80
70
60
50
40
30
20
10
0
0 50 100 150 200 250 300
Adsorption Yield (%)
Times (min)
Process governed by the pseudo
second-order model, the application
of intra-particle diffusion model
showed that the adsorption of the
BM on bottom ash is controlled by
different phenomena (external
diffusion, internal diffusion and
fixation process of BM on active
sites of the adsorbent).

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