Removal of Organic Micropollutants by Coagulation in Wastewater Treatment
Tingyun Zhou
For the degree of
Master of Science in Civil Engineering Date of submission: June 2011 Date of defense: June 30, 2011
Acknowledgements First and foremost, I would like to thank my thesis supervisor Prof.dr.ir. Luuk C. Rietveld and Dr.ir. Jaap de Koning from sanitary engineering department of TU Delft for allowing me join OPTIMIX project, for their expertise, kindness, and most of all, the patience. A special thanks to Dr.ir.S.I.de Castro Lopes from Nalco Europe for all the guideness and advice. Also my great thanks and appreciation goes to ir. A. D. Schuit and ir.R.P. Andeweg Patrick from water lab of TU Delft, who helped and guided me, ―Miss ―Miss trouble‖ trouble‖ , through all the equipments, methods of laboratory examination and transportation. I would also like to thank Jeroen de Jong and Dr. Corine J. Houtman from Het Waterlaboratorium, ir. David de Ridder and Dr.ir.A.R.D.Verliefde from TU Delft who guided and helped me with the sample analysis which was the most tricky part during my thesis work. Many appreciations also goes to my dear colleagues in the project, ir.Guido Kooijman and ir. M.F.Mohd Amin, my work won‘ won‘ t be completed without your daily support. Finally, I owe special gratitude to my family and friends for contimuous and unconditional love and support.
Abstract The
thesis
study
aimed
to
investigate
the
application
of
organic
polymers
as
coagulants/flocculants to remove the organic micropollutants from raw waste water. Understand the mechanisms of pharmaceuticals removal by coagulation/flocculation. Determine what organic flocculants are effective in removing different kinds of organic micro pollutants, what the possibilities for phosphate and dissolved organic carbon (DOC) removal are. During the proposed study an inventory was made of the experiences with different polymers with respect to the removal of organic micro pollutants and phosphate. Different polymers were selected and jar tests were performed, testing the different polymers under different conditions: mixing condition, dose, pH. Then mechanism tests were performed in 3 types of matrices (tap water, 0.45µm filtered wastewater, raw wastewater) to find the removal mechanism of organic micro-pollutants and relations between the removal and characteristics of polymers/pollutants. It can be concluded that under current conditions polymer worked well on particle removal and phosphorous removals were mainly along with particle removal. However, polymers do not
Nomenclature BOD
Biochemical Oxygen Demand
[mg/l]
COD
Chemical Oxygen Demand
[mg/l]
C s
Concentration of micro-pollutant in the sediments/sludge
[ng/mg]
C w
Concentration of micro-pollutant in dissolved phase
[ng/l]
DOC
Dissolved Organic Carbon
[mg/l]
DWA
Dry weather flow
f oc
The fraction by weight of organic C in the sediments/sludge (TOC/TSS)
HMW
High molecular weight
HWL
Het Waterlaboratorium
K d
Sorption isotherms
[l/mg]
K oc
Organic-C normalized partition coefficient
[-]
K ow
Octanol-water partition coefficients
[-]
LMW
Low molecular weight
[-]
Log D pH7.4
pH corrected logK ow at pH 7.4
[-]
MMW
Mid molecular weight
[-]
MW
Molecular weight
[g/mol]
N-total
Total Nitrogen
[mg/l]
P-total
Total Phosphorous
[mg/l]
SPE
Solid phase extraction
[m3 /day] [-]
List of Figures Figure 1 a) Adsorptive coagulation, b) Bridging flocculation ....................................................... 3 Figure 2 Overdosing of polymers results in destabilization ......................................................... 3 Figure 3 Jar test equipment ........................................................ ........................................... 11 Figure 4 (a) Location of Leiden ZW on the map of the Netherlands; (b) View of Leiden ZW (from Google map) ........................................................................................................ ................. 14 Figure 5 The photo of Filtration setup ................................................. ................................... 15 Figure 6 Turbidity for 15 flocculants in terms of dosage (25~500ppm) ..................................... 22 Figure 7 Turbidity for 15 flocculants at 12.5ppm dosage .......................................................... 22 Figure 8 Turbidity for Coagulants+7757 in terms of dosage ..................................................... 22 Figure 9 Turbidity for flocculants under various rapid mixing conditions.................................... 25 Figure 10 Performance of 4 flocculants under various rapid mixing conditions........................... 26 Figure 11 Turbidity for 4 flocculants under various slow mixing conditions ................................ 26 Figure 12 Performance of 4 flocculants under 5mins/200rpm rapid mixing and various slow mixing ........................................................................................................ .......................... 27 Figure 13 Turbidity removals for Nalco 71403 under various mixing conditions ......................... 28 Figure 14 Turbidity removals for CORE SHELL 71305 under various mixing conditions ............... 28 Figure 15 Turbidity removals for 77135+ An/Nonionic flocculants under various mixing conditions (50ppm+5ppm) ........................................................................ ............................................ 29 Figure 16 Turbidity removals for all the combinations (50ppm+5ppm) ..................................... 29 Figure 17 Turbidity, Ptot and PO4-P removals by Nalco 71403 .................................................. 32 Figure 18 Turbidity and PO 4-P removals by CORE SHELL 71305 ............................................... 32 Figure 19 Turbidity for 77135 combinations under lower dosage .............................................. 33 Figure 20 Lower dosage coagulant screening test graph .......................................................... 33 Figure 21 The turbidity result of anionic/cationic combination dosage test ................................ 33
List of Tables Table 1 Applicable organic polymers for flocculation of wastewater ............................................ 4 Table 2 Literature information on mixing times and intensity when dosing polymers ................... 5 Table 3 Origin, type and pathways of organic micro pollutants (Hollender, 2008) ........................ 6 Table 4 The characteristics of tested polymers ........................................................................ 13 Table 5 Water quality of Leiden Zuidwest from 2007.8 to 2008.8 ............................................. 14 Table 6 The properties of selected compounds ....................................................................... 16 Table 7 Overview of jar test setting in this study .................................................... ................. 18 Table 8 Sample information and mixing conditions of Setting A ................................................ 21 Table 9 Sample information of Setting B ................................................................................. 24 Table 10 Mixing conditions of Setting B .................................................................................. 24 Table 11 Sample information of Setting C ..................................................... .......................... 31 Table 12 Mixing conditions of Setting C .................................................................................. 31 Table 13 Optimal dosage and the performance for each candidate ........................................... 35 Table 14 Sample information of Setting D ..................................................... .......................... 36 Table 15 Mixing conditions of Setting D .................................................................................. 36 Table 16 Sample information of mechanism tests .................................................................... 38 Table 17 Mixing conditions of mechanism tests ...................................................... ................. 38 Table 18 Sample information for pharmaceutical analysis ........................................................ 40 Table 19 Measuring concentration of 15 compounds in pharmaceutical working solution ........... 41
Contents ACKNOWLEDGEMENTS ABSTRACT
........................................................................................................................... I
.................................................................................................................................................. II
NOMENCLATURE
.................................................................................................................................... III
LIST OF FIGURES.................................................................................................................................... IV
LIST OF TABLES CONTENTS
........................................................................................................................................V
................................................................................................................................................ VI
1. INTRODUCTION
.................................................................................................................................. 1
2. THEORETICAL BACKGROUND ......................................................................................................... 2 2.1 COAGULATION /FLOCCULATION MECHANISMS ........................................................................................... 2 2.1.1 Electrostatic coagulation .......................................................................................................... 2 2.1.2 Precipitation coagulation (or sweep coagulation) ................................................................ 2 2.1.3 Adsorptive coagulation ............................................................................................................ 2 2.2 ORGANIC POLYMERS .............................................................................................................................. 3 2.2.1 Organic polymer for coagulation/flocculation in w ater treatment ..................................... 3 2.2.2 Characterization of organic polymers .................................................................................... 4 2.2.3 Category ..................................................................................................................................... 4 2.2.4 Polymer dosage ........................................................................................................................ 4 2.3 COAGULATION /FLOCCULATION MIXING CONDITIONS FOR POLYMERS ........................................................ 5 2.4 ORGANIC MICRO-POLLUTANTS ................................................................................................................ 5 2.4.1 Definition and origins of organic micro-pollutants 5
4.2.1 General ......................................................................................................................................23 4.2.2 Testing conditions ...................................................................................................................24 4.2.3 Polymer dosage .......................................................................................................................24 4.2.4 Sample analysis .......................................................................................................................24 4.2.5 Results .......................................................................................................................................24 4.2.6 Conclusion ................................................................................................................................30 4.3 SETTING C – OPTIMAL DOSAGE TESTS ..................................................................................................30 4.3.1 General ......................................................................................................................................30 4.3.2 Testing conditions ...................................................................................................................31 4.3.3 Polymer dosage .......................................................................................................................31 4.3.4 Sample analysis .......................................................................................................................31 4.3.5 Results .......................................................................................................................................31 4.3.6 Conclusion ................................................................................................................................35 4.4 SETTING D – PH VARYING TESTS ..........................................................................................................35 4.4.1 General ......................................................................................................................................35 4.4.2 Testing conditions ...................................................................................................................35 4.4.3 Polymer dosage .......................................................................................................................36 4.4.4 Sample analysis .......................................................................................................................36 5.4.5 Results and conclusion ...........................................................................................................36 5. REMOVAL MECHANISM EXPERIMENTAL RESULTS
................................................................38
5.1 GENERAL ..............................................................................................................................................38 5.2 TESTING CONDITIONS ...........................................................................................................................38 5.3 PHARMACEUTICALS SPIKING ..................................................................................................................38 5.4 POLYMER DOSAGE AND PRICE ................................................................................................................39 5.5 S AMPLE ANALYSIS .................................................................................................................................39 5.6 R ESULTS ..............................................................................................................................................39 .......44 5.7 DISCUSSIONS AND CONCLUSIONS
1. Introduction Waste water treatment plants are an important source for emerging substances in the environment. Problems are caused by organic micro-pollutants (pharmaceuticals, pesticides and other endocrine disrupting compounds) and heavy metals. The degree of removal of these compounds is low when they are dissolved or attached to colloids. Different methods are available to remove these compounds such as ozonation and activated carbon filtration. However, these technologies are expensive in investment and operation. Therefore, it is proposed to investigate the possibility to remove the organic micropollutants by coagulation/flocculation. The advantage of this method is that it can be combined with phosphate removal and that sludge removal can be enhanced during primary settling. When organic flocculants (polymers) are used, this sludge can be used for energy regeneration. The thesis study aimed to investigate the application of organic polymers coagulants/flocculants to remove the organic micropollutants from raw waste water.
as
Understand the mechanisms of pharmaceuticals removal by coagulation/flocculation. Determine what organic flocculants are effective in removing different kinds of organic micro pollutants, what the possibilities for phosphate and dissolved organic carbon (DOC) removal are. The cost and difficulty of sample analysis are taken into account to determine the organic pollutants to be tested. It is not practical to study all types of organic micro-pollutants in the wastewater. So pharmaceutical were decided to be the purpose removal objects in this study. This study was included in a research project OPTIMIX and it was developed by TU Delft, The
2. Theoretical Background 2.1 Coagulation/flocculation mechanisms Colloidal particles found in wastewater typically have a net negative surface charge. They are stabilized due to the presence of an electrical double layer of ions and the resulting negative zeta potential. The viable method to remove colloids from wastewater is to destabilize the suspension using chemicals. Regarding these destabilization and attachment processes, a general distinction is made between coagulation and flocculation (van Nieuwenhuijzen, 2002). Coagulation indicates the process of charge neutralization resulting in destabilization of the particles, while the term flocculation is used to indicate the process of complex formation that is succeeding the destabilization. Three main mechanisms are described below:
2.1.1 Electrostatic coagulation Electrostatic coagulation is the most important process when metal salts are applied. It is caused by an increase in the electrolyte concentration in the wastewater suspension when adding the metal salts. The amount of counter ions present in the diffuse part of the electrical double layer in the stable colloidal suspension increases, which causes destabilization of the particles in suspension (van Nieuwenhuijzen, 2002). After dosing coagulant, the exterior of the colloidal particle is destabilized and can collide with other particles into removable flocs. If high dosages of coagulants are added, the concentration of ions in the diffuse layer may increase to such a level that the zeta potential shifts to a positive charge. In that case, the particles will be positively charged and again be colloidal stable in suspension (Tchobanoglous et al., 2003).
Figure 1 a) Adsorptive coagulation, b) Bridging flocculation
However, there are some disadvantages such as higher costs in particular situations and environmental factors, and greater sensitivity to incorrect dosage.
2.2.2 Characterization of organic polymers Organic polymers are generally characterized by two main properties: their molecular weight and the amount of ionic charge. Molecular weight (WM) The molecular weight is an indication for the amount of monomers and thus the length of the polymer chain. The organic polymers could be divided in low molecular weight (LMW), mid molecular weight (MMW) and high molecular weight (HMW) corresponding to MW values in the ranges: <105, 105-106 and >106 (Bolto et al., 2007). Charge density Polymers can be cationic, anionic and non-ionic. The charge density of the polymer indicates the amount of charge available to accomplish particle destabilization and flocculation. Previous research showed that cationic organic polymer can be used for flocculation of raw municipal wastewater. However, the addition of an anionic polymer did not show significant turbidity removal (van Nieuwenhuijzen, 2002). Others Additional to the molecular weight and the charge density, the structure of the polymer is import. Besides the linear configuration, polymers can be manufactured cross-linked or branched. Polymers are especially used in sludge dewatering by centrifuges because of their ability to resist high shear forces.
2.3 Coagulation/flocculation mixing conditions for polymers The coagulation-flocculation process is influenced by raw water characteristics, temperature, pH, coagulant type and dose. However to avoid a poor performance the most important parameters of mixing design must be considered: velocity gradient and mixing time. In table 2 there is the literature information on mixing times and velocity gradients for jar test when dosing organic polymers. Table 2 Literature information on mixing times and intensity when dosing polymers Rapid mixing time and intensity
Application Jar test with municipal wastewater Jar test with municipal wastewater Jar test with municipal wastewater Jar test with municipal wastewater Jar test with industrial wastewater Jar test with HA solution Jar test with HA solution Jar test with HA solution
Slow mixing time and intensity
Reference
1-2min
10-25min
Udaya Bhaskar and Gupta (1987)
20s-120s,800s -1
3min, 50s-1
van Nieuwenhuijzen (2002)
2min, 300rpm
10min, 50rpm
Pinto (2008)
3min, 150rpm
5min, 50rpm
Carballa.et al. (2005)
1min, 100rpm
2min, 25rpm
Torres.et al.(1997)
2min, 250rpm 1.5min, 102.5s
10min, 30rpm -
15min, 11.8s
Hankins (2006)
-
1
1
Wei (2009)
3min, 200rpm
25min, 35rpm
Moussas (2009)
Table 3 Origin, type and pathways of organic micro poll utants (Hollender, 2008) Pathways in the environment
Source
Substance groups
Urban settlements
Personal care products, human pharmaceuticals, detergents, chemicals used in construction business (dyes, lacquer, binder, wood preservatives), flame retardants, pesticides, biocides
Wastewater Diffuse Landfill site
Pesticides(insecticides, herbicides, fungicides),veterinary pharmaceuticals
Wastewater Diffuse
Industry
Industrial chemicals (polymers, dyes, varnishes, oxidants, reductants, detergents, corrosion inhibitors, biocides)
Wastewater Landfill site
Traffic
Ingredients of motor oils, lubricants, combustion products
Diffuse Landfill site
Agriculture
2.4.2 Organic micro-pollutants in aquatic environments In aquatic environment, organic micropollutants can exist in a variety of forms: as a freely dissolved phase, as a colloidal phase or associated with sedimentary material (Warren et al., 2003). Associated with suspended solid particles
The relationship between K ow and K oc values has been found by several authors (Kenaga and Goring, 1980; Lyman et al., 1982; Karickhoff, 1984; Grathwohl, 1990) to be of the form: log K oc= a log K ow – y Thus in theory it should be possible to predict K d values from octanol-water partition coefficients and sediment fractional organic-C contents, and in general it is found that the more hydrophobic compounds (with the highest K ow) do exhibit the highest K oc(Warren et al., 2003). Despite strong direct interactions with sediments, charged or highly-polar compounds still generally exhibit lower K d values than non-polar non-ionic compounds, except on bare mineral surfaces, owing to their much higher water solubility. Cationic compounds generally interact much more strongly with sediments than anionic ones, since ionisable organic-matter moieties and mineral surfaces are generally neutral or negatively charged over the pH range found in the environment. Interactions of micro-organics with dissolved organic matter Natural colloidal organic matter, often referred to as dissolved organic C (DOC), has two main effects on the distribution of micro-organic pollutants between aqueous and sediment-bound phases. These are ‗solubility enhancement‘ and the ‗solids concentration effect‘ (Warren et al., 2003). Solubility enhancement is the reduction in the observed solid-solution distribution coefficient, K d, in the presence of DOC. This makes a compound appear to be more soluble in water, and reduces the total sediment- sorbed amount. The reason for the enhancement is that the contaminants can also partition into hydrophobic domains in colloidal organic matter (Warren et al., 2003).
2.4.4 Properties of organic pollutants Several solute properties that influence organic pollutants adsorption are discussed. These properties include solute hydrophobicity, partition coefficient, polarizability, molecular structure. Solute Hydrophobicity K ow Solute hydrophobicity is often represented by the octanol –water partitioning coefficient (log K ow) (de Ridder et al., 2010). Large K ow values are characteristic of large hydrophobic molecules which tend to be associated with solid organic matter while smaller hydrophilic molecules have low K ow values [ICON, 2001].
Several authors have tried to directly relate log K ow to observed adsorption rates. Good relations between log K ow and adsorption rates were found in a system containing hydrophobic solutes and a hydrophobic adsorbent. A poor correlation was found when hydrophobic partitioning is less relevant, i.e., when the solutes are small, hydrophilic and/or charged/polar [de Ridder et al., 2010]. For ionic solutes, log K ow values were corrected for pH with respect to their H + dissociation/ uptake. The pH-corrected log K ow values are referred to as log D (distribution coefficient). Log D values can be determined from log K ow values and the pKa values of the solute. For neutral solutes, log K ow=log D; for ionic solutes log D < log Kow (de Ridder et al., 2010).
2.4.5 Statutory standards of micro-pollutants Actual statutory standards for effluent of wwtp are not yet available for most organic micropollutants. There is a Dutch standard refers to the MAC (maximum permissible risk) for surface water (source: RIVM, environmental quality, March 2009). The European standard is about the standards for priority substances of the WFD (Source: Agreement priority substances, Council of the European Union, June 23, 2008). However, for all used below norms emphasize that these are standards for surface water and not standards for the effluent of WWTP's. The MAC value of different substances for surface water coul d be used to compare with the concentrations of the testing result in this study.
2.4.6 Organic micro-pollutants removal possibility by polymers Removal pollutants by adsorption to particles The sorption of organic contaminants onto the solids is determined by physicochemical processes and can be predicted for individual compounds by the octanol-water partition coefficient (K ow). During the jar test, hydrophobic contaminants may partition onto settled solids particles and compounds can be grouped according to their sorption behavior based on the K ow value as follows:
Log K ow < 2.5 low sorption potential
Log K ow > 2.5 and < 4.0 medium sorption potential
Log K ow > 4.0 high sorption potential
Removal pollutants by binding with dissolved organic matter such as humic acid
-
During wastewater treatment, the compounds that consist of aromatic rings such as benzo[a]pyrene, benzo[g,h,l]perylene, benzo[k]fluoranthene, mirex, benzo[b]fluranthene, and benz[a]anthracene, showed a high removal of more than 85% by flocculation with alum and iron salts. However, the compounds such as diazepam, diclofenac, and meprobamate, indicated the lowest removal (less than 10%). Alum as a coagulant resulted in a slightly better removal compared to ferric chloride coagulants. EDCs or PPCPs are removed by partially adsorbing on particles in water and metal hydroxide particles formed during flocculation (Westerhoff et al., 2005).
-
Dissolved humic acid (DHA) can be used as a complexing agent to remove hydrophobic contaminants from water by complexation-flocculation process. Flocculation of DHA at concentrations of 1-50 mg/l OCHA was highly efficient with both alum and ferric chloride. The proposed process is effective in removing pollutants of medium to high hydrophobicity (log K ow > 4.5) (Rebhun et al., 1998).
-
Carballa et al. (2005) indicates that, in the sewage, compounds with high sorption properties (high logK d values), such as musks (Galaxolide and Tonalide) and Diclofenac, are significantly removed during coagulation –flocculation with efficiencies of 70% in the temperature range of 12 –25 1C. Lipophilic compounds, like musks, are mainly absorbed on the lipid fractions of the sludge, while acidic compounds, like Diclofenac, are mainly adsorbed due to electrostatic interactions. Compounds with lower K d values, such as Diazepam, Carbamazepine, Ibuprofen and Naproxen, were reduced to a lesser extent (Diazepam and Naproxen), up to 25%, or not affected at any condition tested (Carbamazepine and Ibuprofen) (Carballa et al., 2005).
-
Suarez et al. (2009) showed similar limited removal in hospital wastewaters. Highest efficiencies have been measured for musk compounds (HHCB, AHTN and ADBI) (>90%) which was attributed to their strong lipophilic character that enhanced their removal by
3. Materials and Methods During the proposed study an inventory was made of the experiences with different polymers with respect to the removal of organic micro pollutants and phosphate. Then different polymers were selected and jar tests were performed, testing the different polymers under different conditions: water quality, mixing condition, dose, pH. After that, the results of the experiments were elaborated and find the removal mechanism of organic micro-pollutants and relations between the removal and characteristics of polymers/pollutants.
3.1 Jar test procedure To simulate conventional clarification, coagulation, flocculation and sedimentation steps were performed in a standard jar test apparatus according to KIWA (Figure 3). It consisted of six beakers with a volume of 1.8 L and stirrers, which could be adjusted to the same stirring conditions for all the beakers. The beakers were filled with 1.8 L of sample and the coagulant/flocculant was added simultaneously to all beakers.
Finally the suspension was allowed to settle during a sett ling time of 15/20 min.
3.2 Coagulants/flocculants General In this research work, 20 different polymers consisting of 10 cationic flocculants, 4 anionic flocculants, 1 nonionic flocculant and 5 cationic coagulants were tested. They were all provided by Nalco company.The overview of each tested polymer are shown in Table 4. Price of the polymers -
Price ratio of coagulant versus cationic flocculant: from approx 1:2 up to 1:2.5 (the higher the cationic charge the higher the cost)
-
Price ratio coagulant versus anionic flocculant: approx 1:1,5 (the higher the anionic charge the higher the cost, but less significant than with cationics)
Polymer stock solution making Polymer solutions were prepared by dissolving the basic polymer emulsions at least 30mins before the experiments that could be immediately added to the wastewater samples. These stock solutions could be kept for one day. The concentration of polymer stock solution was various in different settings. Dosage The dosage of polymers depended on the quality of sample. In this study, dosage range of coagulant/flocculant was from 0.5 ppm to 200 ppm. Note that those dosing volumes ranging
Table 4 The characteristics of tested polymers Type
Cationic flocculant
Anionic flocculant Nonionic flocculant
Coagulant
Code
Active constituents
Appearance
NALCO 71403
Acrylamide based co-polymer
NALCO 71406
Acrylamide based co-polymer
NALCO 71413
Acrylamide based co-polymer
CORE SHELL 71305
Acrylamide based co-polymer
MW
Off-white liquid
Emulsifiable
Medium
High
Off-white liquid
Emulsifiable
Medium
High
0,01~0,05%
<1%
Emulsifiable
Medium~high
High High~very high
0,01~0,05%
<0.5%
Dispersible
Medium
0,5~2%
Medium
0,5~2%
CORE SHELL 71303
Acrylamide based co-polymer
ULTIMER 7752
Acrylamide based co-polymer
White liquid
ULTIMER 1460
Acrylamide based co-polymer
Milky white
Completely
ULTIMER 1454 ULTIMER 71456
Acrylamide based co-polymer Acrylamide based co-polymer
White/opaque liquid White liquid
Completely Completely
Low Medium
High High
ULTIMER 71458 NALCO 71601
Acrylamide based co-polymer Acrylamide based co-polymer
White liquid Off-white liquid
Completely Emulsifiable
Medium Low
High High
NALCO 71603
Acrylamide based co-polymer
Off-white liquid
Emulsifiable
Low
NALCO 71605 ULTIMER 7757
Acrylamide based co-polymer Acrylamide based co-polymer
Off-white liquid Milky white
Emulsifiable Completely
Medium Medium
NALCO 71760
Acrylamide based homo-polymer
Off-white liquid
Insoluble
Amber liquid Light yellow liquid Pale yellow~amber liquid
Completely Completely
Polyelectrolyte
Recommended stock solution preparation <1%
Charge
Off-white liquid Opaque off-white emulsion Off-white emulsion
NALCOLYTE 7135 NALCO 8105 PLUS CAT-FLOC 8103 PLUS
Typical concentration in wastewater
Solubility
Low
0,2~0,5%
Medium
NALCO 77135
Aromatic heterocyclic compund, vegetable originated
Dark brow clear liquid
Completely
NALCO 8190
Polyampholytic
Clear liquid
Completely
0,2~0,5%
0,01~0,1% 0,01~0,1% 0,01~0,05%
0,01~0,1% <1%
High
0,01~0,05%
<1%
High Medium
0,01~0,05% 0,5~2%
High
<1% 1~100ppm It depends
High
Medium~ High
Medium
Medium
It depends
High
1~10ppm
1%
13
3.3 Water samples Raw wastewater from the municipal wastewater treatment plant of ―Leiden Zuidwest‖ was used. WWTP Leiden Zuid-West treats the water of 126,000 inhabitants living in the area of Leiden Zuid-West, Voorschoten and Zoeterwoude-Dorp. The average daily flow is 24,000 m 3. At the WWTP first of all removal of coarse solids takes place followed by nitrification and denitrification combined with chemical phosphorous removal and finally sedimentation (Scherrenberg et al.,2008 ).
Leiden Zuidwest wwtp
Inlet
Outlet
0.45μm filtrate
0.45μm filter
1μm filter
Raw waste water tap
Figure 5 The photo of Filtration setup Tap water During the mechanism tests, tap water was also needed which was taken directly from the drinking water tap in the lab at wwtp Leiden ZW.
3.4 Pharmaceuticals
Table 6 The properties of selected compounds (MW, log K ow, log D,polarizability, sum HB were deried from Chemspider; pKa were deried from Phys Prop Database, 2004;concentration were deried from Broninventarisatie KRW-stoffen, 2009) NO.
Compounds
MW (g/mol) 266.3
log K ow ow () 0.16
log DpH 7.4 (-) -1.66
pK a (-)
DWA influent (µg/l)
DWA effluent (µg/l)
RWA influent (µg/l)
RWA effluent (µg/l)
atenolol1
2
bezafibrate2
361.8
4.25
-0.14
n.a
38.05
7
0.21
0.05
0.08
0.05
3
carbamazepine2
236.3
2.45
1.895
n.a.
27.625
4
0.9
0.77
0.25
0.26
4
clofibric acid1
214.7
2.57
-0.9
n.a
21.11
4 0.35
0.32
0.1
0.19
2
9.6
diclofenac
296.2
4.51
1.437
6
gemfibrozil2
250.3
4.77
1.77
7
ibuprofen2
206.3
3.97
0.582
8
ketoprofen2
254.3
3.12
0.41
9
metformin1
129.2
-1.40
-3.82
10
metoprolol2
267.4
1.88
-0.06
n.a
11
naproxen2
242.2
3.18
0.347
4.15
12
paracetamol1
151.2
0.46
0.474
13
propranolol1
259.4
3.48
0.785
2
14
sulfamethoxazole
253.3
0.89
-0.2
15
trimethoprim2
290.3
0.91
0.473
2
sum HB da
1
5
1
Polarizability (10-24 cm3) 29.438
4.15
9
30.339
5
28.5
4
1.02
0.33
0.33
0.22
4.91
24.093
3
5.95
0.08
1.9
0.11
4.45
28.462
6
n.a
n.a
<0.03
<0.03
13.22
10
30.55
7
1.8
1.5
1.06
1
26.372
4
3.45
0.24
1.13
0.18
9.38
16.811
4
9.42
31.312
5 9
0.39
0.12
0.12
0.08
11
0.28
0.16
0.08
0.1
n.a. 7.12
24.75 31.817
Frequently detected from Dutch wastewater (van Beelen, 2007) Present in Leiden ZW (Broninventarisatie KRW-stoffen, 2009)
16
3.5 Jar test experiments 5 phases of jar test experiments were performed: Preliminary experiments －
Setting A -- Screening test (with raw wastewater) Select 6~8 candidates from the 20 different polymers (10 cationic flocculants, 4 anionic flocculants, 1 nonionic flocculant and 5 cationic coagulants).
－
Setting B -- Optimal mixing condition test (with raw wastewater) Perform the candidates that selected from Setting A under varying mixing conditions and obtain the optimal mixing conditions for each candidate. Then decide 4 final candidates for the further research.
－
Setting C -- Optimal dosage test (with raw wastewater) Vary the dosage for the 4 candidates under the optimal mixing condition got from Setting B to obtain the optimal dosage.
－
Setting D -- pH various test (with raw wastewater) Compare the turbidity removal efficiency differences with varying pH (increase/decrease 1 PH unit).
Mechanism experiments
Table 7 Overview of jar test setting in this study
setting
A
B
Sample
PH
Screening tests (20 polymers) Optimal mixing condition
4 flocculants and 15 coagulant+flocculant combinations
Rapid varing Slow varing
C
Optimal Dosage
2 flocculants and 2combinations
D
PH varying tests
2 flocculants and 2 combinations
Mechanism tests
2 flocculants and 2 combinations
Raw wastewater
Raw +substances Filtered raw +substances Tap water +substances
Total
depend on sample quality
Rapid mixing time(min)
Stirrer velocity 1 (rpm)
G-value 1(s-1)
Slow mixing (min)
Stirrer velocity 2 (rpm)
G-value 2 (s-1)
2
300
700
5
30
24
2/5
200/300
400/700
3
30
24
2 5
200 200
400 400
5/10 1/3/5/10
30/50 30
24/50 24
Settling time (min)
Number of tests
10 15 41
Jar test performed under optimal mixing condition of each candidate obtained from Setting B
19
PH variation
performed under optimal mixing condition and optimal dosage
2
depend on sample quality
performed under optimal mixing condition and optimal dosage
4
Remarks
Select best polymers Obtain optimal mixing condition Obtain optimal dosage See the pH impact Understand the adsorption mechanism in different types of sample
76
18
3.6 Analyses Below it is described the analyses performed on the supernatant of samples after the jar tests. The methods and definitions presented are based on Standard Methods (1998), Tchobanoglous et al (2003) and Merck procedures information review. Turbidity Turbidity in water traduces it quality regarding the presence of suspended solids (SS) and colloidal matter, though a correlation of turbidity with the weight or particle number concentration of suspended matter is difficult. However, this parameter has been used as the primary indicator of mainly general process efficiencies. Turbidity was measured with 2100N Turbidity meter sell by HACH. pH The measurement of pH is defined as the determination of hydrogen ions activity in a solution, an important quality parameter of wastewater. Mostly all steps include in wastewater treatment, e.g., acid-basic neutralization, water softening, precipitation, coagulation, disinfection and corrosion control are a function of pH-value. pH was measured with a pH meter (pH 197i from WTW) consisting of a potentiometer with a temperature-compensating device and accurate to 0.1 pH unit with a range from 0 to 14. Temperature The measurement of temperature is required in order to control the processes involved
3.7 Sample preparation For pharmaceutical analysis, before being sent to HWL, the samples were prepared (solid phase extraction) in the lab at TU delft. The samples were collected in amber glass bottles prewashed by demi water. Solid phase extraction (SPE) was conducted on a SPE Vacuum Manifold: －
SPE cartridge (Oasis HLB 6cc/200mg) was conditioned with 2*5 ml methanol and 5 ml demi water.
－
Filtration column (Baker Disposable filtration column 6ml) filling with 1cm thick sea sand was connected to the SPE cartridge. After that, wet the sand bed with demi water.
－
Sample (100 ml) was introduced to the filtration column and SPE cartridge via a PTFE tube.
－
After being washed with 5ml of 5.0% methanol solution, the cartridge was dried under vacuum for half minute and eluted with 2*4 ml methanol at a flow rate of 12 ml/min.
－
The extracts were stored at 4℃ and then sent to HWL for analyze.
4. Preliminary Experimental Results Jar tests were conducted to determine the feasibility and effectiveness of organic polymers for flocculation of municipal wastewater.
4.1 Setting A – Screening tests 4.1.1 General There are 20 polymers with different characristic (shown in Table 4) tested during the screening test. Turbidity has been used as the primary indicator of overall process efficiency (Abdessemed et al, 2000). Based on the turbidity removal efficiency, 5 candicates were selected to be tested during the further study.
4.1.2 Testing conditions All the polymers were tested under the conditions presented in table 8: Table 8 Sample information and mixing conditions of Setting A Experiment date 2010/7/21~
pH
T (◦C)
Turbidity (NTU)
7.29
21.52
133.44
Rapid mixing time(min)
Stirrer velocity 1 (rpm)
G-value 1(s-1)
Slow mixing (min)
Stirrer velocity 2 (rpm)
G-value 2 (s-1)
Settling time (min)
Figure 6 Turbidity for 15 flocculants in terms of dosage (25~500ppm)
Flocculants It can be concluded from Figure 6 and 7 that cationic organic polymers performed better than an/nonionic polymers on turbidity removal with raw wastewater. In Figure 6, 15 polymers could be distingished clearly into two groups at and above the dosage of 50 ppm: cationic polymers (higher than 50% turbidity removal) and anionic polymers (lower than 50% turbidity removal). Most of the cationic flocculants have the best turbidity removal at the dosage of 25ppm or 50ppm. The turbidity removal decreased at the dosage of 125ppm, which is because of the overdose of polymer resulting in destabilization of particles. According to the criterias mentioned above, 6 candidates were selected: -
Nalco 71403, Nalco 71406: best performing products at lower dosages (25ppm and 50ppm).
-
CORE SHELL 71305, CORE SHELL 71303: forming larger flocs than other polymers, performing the best at 50ppm dosage (above 90% turbidity removal). Because of a higher dosage than other polymers during the experiments, only tubidity removal at 50ppm dosage could be compared with other polymers. In the further setting, these two candidates were tested at lower dosage.
Coagulants Figure 8 showed that, combining with flocculant (25ppm of ULTIMER 7757 ), the turbidity removal of most of combinations increased with the increasing of dosage except Nalco 8190. The best performance of Nalco 8190 was at the dosage of 62.5ppm.
4.2.2 Testing conditions The candidates were tested under the conditions presented in table 9 and table 10: Table 9 Sample information of Setting B Experiment date
pH
T (◦C)
Turbidity (NTU)
2010/7/28~2010/8/6
7.25
20.2
106.2
2010/9/15~2010/9/16
7.49
18.7
46.5*
2010/9/20~2010/10/5
7.36
18.6
93.2
* The turbidity during 2010/9/15~9/16 was much lower than others was because the heavy rain during that week.
Table 10 Mixing conditions of Setting B Setting
Rapid mixing time(min)
Stirrer velocity 1 (rpm)
G-value 1(s-1)
Slow mixing (min)
Stirrer velocity 2 (rpm)
G-value 2 (s-1)
Settling time (min)
Rapid mixing various
2/5
200/300
400/700
3
30
24
15
2
200
400
5/10
30/50
24/50
15
5
200
400
1/3/5/10
30
24
15
Slow mixing various
Figure 9 Turbidity for flocculants under various rapid mixing conditions It can be seen from Figure 9 that the turbidity removal under 5 mins rapid mixing was slightly better than 2 mins rapid mixing for each candidate. It is mainly because the polymer needed
Figure 10 Performance of 4 flocculants under various rapid mixing conditions Slow mixing Figure 11 shows the results of the experimental runs for 4 flocculants in terms of dosage under varying slow mixing conditions.
Figure 12 Performance of 4 flocculants under 5mins/200rpm rapid mixing and various slow mixing
Figure 13 Turbidity removals for Nalco 71403 under various mixing conditions
Figure 15 Turbidity removals for 77135+ An/Nonionic flocculants under various mixing conditions (50ppm+5ppm) For the rapid mixing, the turbidity removal under 5/200,5/30 was much better than 2/300,5/30 for all the combinations. It indicated that under the same slow mixng, the rapid mixing did influence the performance of these combinations. 5mins rapid mixing is better than those under 2mins. Since the abnormal performance of polymer on Aug. 6th (2/300,5/50; 5/200,5/50; 5/300,5/50), the conclution (5mins rapid mixing is better than 2mins) conducted
Under mixing condition 5/200, 3/30, 3 anionic combinations and 4 cationic combinations could achieved good turbidity removal (above 80%). The best combination was 77135+7757 with a turbidity removal of 87%. Under 5/300, 5/50 mixing condition, 77135+71406 and 77135+71413 removed turbidity up to 93% and 94% while the best anionic combination (77135+7757) removed 86% turbidity. Coagulant Nalco 77135 From Figure 16, it can be seen that using coagulant only also remove turbidity above 80% under 5/300, 5/50 mixing condition. However, the flocs formed by coagulant alone were smaller and looser than the flocs formed by the combination. So these flocs needed more time to be settled.
4.2.6 Conclusion 1. Optimal mixing condition For Nalco 71403, 5/200 rapid mixing, 5/30 slow mixing was the best mixing condition for Nalco 71403. The turbidity removal for CORE SHELL 71305 under 5mins rapid mixing is better than those under 2mins. 5/200 rapid mixing, 3/30 slow mixing was the optimal mixing condition for CORE SHELL 71305. For all the combinations, 5mins rapid mixing is better than those under 2mins. Under mixing condition 5/200, 3/30, anionic combinations could achieved good turbidity removal (above 80%). The best combination was 77135+7757 with a turbidity removal of 87%. Under mixing condition 5/300, 5/50, cationic combinations removed turbidity up to 94%.
dosage. So new screen tests of coagulant were needed at the lower dosage. The new lower dosage combinations were tested when the best lower dosage coagulant was selected.
4.3.2 Testing conditions The candidates were tested under the condition presented i n table 11 and 12: Table 11 Sample information of Setting C Setting
Experiment date
PH
T (◦C)
Turbidity (NTU)
For flocculants
2010/11/08~2010/11/10
7.69
15.5
65.9*
For combinations
2010/11/17~2010/11/30
7.66
15.3
75.1*
* The turbidity much lower than Setting A was because the rain during that experiment days.
Table 12 Mixing conditions of Setting C Setting
Rapid mixing time(min)
Stirrer velocity 1 (rpm)
G-value 1(s-1)
Slow mixing (min)
Stirrer velocity 2 (rpm)
G-value 2 (s-1)
Settling time (min)
Nalco 71403
5
200
400
5
30
24
15
5
200
400
3
30
24
15
5
200
400
5
30
24
20
5
300
700
5
50
50
20
CORE SHELL 71305 Anionic Combinations Cationic
Figure 17 Turbidity, Ptot and PO 4-P removals by Nalco 71403
Figure 19 Turbidity for 77135 combinations under lower dosage
It is clearly shown that cationic combinations performed better than anionic combinations on turbidity removal. The more coagulant dosing, the better performance. However, for anionic combinations, flocculant dosage at 2ppm didn‘t improve turbidity removal comparing with 1ppm dosage even 0.5ppm dosage. For anionic combinations, 8190+7757 performed better than 8190+71605. The 8190+7757 dosing combination of 15ppm+0.5ppm and 20ppm+0.5ppm were the best with the turbidity removal efficiency of 72% and 74%. For cationic combinations, 8190+71403 performed slightly better than 8190+71406 according to the turbidity removal comparing with the initial value(although the absolute turbidity values of 8190+71406 were lower). The 8190+71413 dosing combination at 15ppm+0.5ppm could result in good turbidity removal (77%) while the best and the most dosing 20ppm+2ppm could remove turbidity 83%. Based on the result in Figure 21, 8190+7757 and 8190+71413 became the final anionic and cationic combination. The other two tests were performed to see the Turbidity, Ptot and PO 4P concentration removal by these two combinations. The results are shown in Figure 22 and 23.
4.3.6 Conclusion 1. Candidate for the further study According to the turbidity removal, 71403 and 71305 were decieded as the 2 final flocculant candidates and 8190+7757(anionic combination) and 8190+71413(cationic combination) were selected as the 2 lower dosage combinations for the PH varing test and Mechanism test. 2. Turbidity and phosphorous removal The flocculants could remove 80%~90% turbidity while the lower dosage combinations could remove 70%~80% turbidity during the experiments. For the phosphorous removal, the flocculants and anionic combination could achieve around 20% removal efficiency. The cationic combination only could achieve around 10% removal efficiency. 3. Optimal dosage for each candidate The turbidity removal was still the main parameter to decide the optimal dosage for each condidate. Meanwhile, the lower dosing principle was also taken into account. For the dosage of flocculants 71304 and 71503, 20ppm would obtain the best turbidity removal among the dosing range of 0.5ppm~25ppm. But considering performance together with sustainable and cost reason, 12.5ppm dosage was good for both flocculants. So 12.5ppm was determined as the optimal dosage for flocculants. For anionic/cationic combinations, 15ppm+0.5ppm was determined as the optimal dosage. Thus, the optimal dosage for each candidate was present in Table 13.
Table 14 Sample information of Setting D Experiment date
pH
T (◦C)
Turbidity (NTU)
2010/12/2
7.65
14.0
109.7
Table 15 Mixing conditions of Setting D Setting
Rapid mixing time(min)
Stirrer velocity 1 (rpm)
G-value 1(s-1)
Slow mixing (min)
Stirrer velocity 2 (rpm)
G-value 2 (s-1)
Settling time (min)
71403/71305
5
200
400
3
30
24
20
Lower dosage combinations
5
300
700
5
50
50
20
4.4.3 Polymer dosage For the flocculants, the dosage of Nalco71403, CORE SHELL 71305 was 20ppm. For the combination dosing, the Nalco 8190 dosage was from 15ppm while the flocculant dosage was 0.5. The concentration of polymer stock solutions during flocculant and lower dosage combinations test were both 0.45%.
4.4.4 Sample analysis
Figure 24 The result of pH various test for flocculants
5. Removal Mechanism Experimental Results 5.1 General Mechanism tests aimed to understand the adsorption mechanism for three pharmaceutical removal possibilities by polymers. -
Adsorption onto particles and dissolved organic matters (with raw wastewater)
-
Attachment onto dissolved organic matters (with filtered wastewater)
-
Adsorption onto polymers (with tap water)
4 polymer candidates (flocculant 71403 and 71305, anionic combination 8190+7757, cationic combination 8190+71413) were tested in 3 types of matrices (Tap water, 0.45μm filtered wastewater and raw wastewater). All the samples were taken in duplicate for higher accuracy.
5.2 Testing conditions The experiments were performed under the conditions presented in table 16 and 17: Table 16 Sample information of mechanism tests Setting Tap water
Experiment date
pH
Turbidity (NTU)
DOC (mg/l)
Ptot (mg/l)
PO4-P (mg/l)
8.45
0.039
3.35
0.039
0.028
5.4 Polymer dosage The dosage of polymers were obtained from Setting C. For the flocculants, the dosage of Nalco71403 and CORE SHELL 71305 in Setting E was 12.5ppm. The concentration of polymer stock solution was 0.45%. For the combination dosing, the coagulant dosage was 15ppm while the flocculant dosage was 0.5ppm. The concentration of 7757 and 71413 stock solution was 0.45% while the concentration of coagulant 8190 stock solution was 1.8%.
5.5 Sample analysis The supernatant water was analyzed for concentration of pharmaceuticals, Turbidity, DOC, PO4-P, P-total, pH immediately after the jar tests.
5.6 Results Dissolved organic carbon (DOC) DOC concentration during the mechanism tests are presented in Figure 26.
The turbidity values increased a little after dosing the polymers into tap water. It was because in the tap water, there was nearly no compounds for flocs formation. In the filtered wastewater sample, the turbidity increased from 25 NTU to 50 NTU. Although the 0.45μm filter removed most of the particles in the raw wastewater, there were some colloidal particles left in the sample. Destabilization occurred when dosing polymer. The higher increasing turbidity by combinations than flocculants indicated that coagulant+flocculant combinations could form more flocs from fine colloidal particles than flocculants in suspended solids free wastewater. In the raw wastewater, the turbidity removal was effective by both flocculants ( 65% removals) and combinations (70% removals). Settling for 0.5 h (jar test with no polymer) can also remove 40% turbidity. Among 4 candidates, anionic combination performed slightly better than others, but the differences were not evident. Phosphorous The Ptot and PO4-P concentrations during the experiments were shown in Fi gure 28.
Table 19 Measuring concentration of 15 compounds in pharmaceutical working solution
atenolol bezafibrate carbamazepine clofibric acid diclofenac
Measuring concentration in working solution (mg/l) 39.26 33.98 32.21 34.73 32.73
Calculated dosing concentration in sample(ng/l) 21812 18877 17896 19294 18185
6 7 8 9
gemfibrozil Ibuprofen ketoprofen metformin
44.41 50.24 32.1 70.14
24669 27913 17831 38966
10
metoprolol
38.48
21380
11 12 13 14 15
naproxen paracetamol propranolol sulfamethoxazole trimethoprim
25.43 36.99 230.59 45.61 52.72
14127 20552 128107 25341 29288
NO.
Compounds
1 2 3 4 5
The measured concentrations of most compounds in working solution were higher than the expected value (27mg/l). Because the expected concentration in working solution (27mg/l) was much higher than the maximum detection limit (1ug/l), the working solution sample should be diluted thousand times. That might result in less reliability of the sample analysis. Moreover, the difference of concentration between non spiking sample and spiking samples for most compounds was 15000ng/l~30000ng/l. It indicated too high concentration in
Figure 31 Relation between average pharmaceuticals removal after
25~50 NTU turbidity increase (a bit better than tap water), no DOC removal and phosphorous removal. In raw wastewater, larger and settleable flocs were formed which resulted in 65%~70% turbidity removal, 12%~17% Ptot removal, 6%~13% PO 4-P removal and no DOC removal after coagulation/flocculation. The results indicate that polymers worked well on particle removal and phosphorous removals were mainly along with particle removal. The higher turbidity increase by combinations in suspended solids free water indicates that coagulant+flocculant combinations can form flocs from dissolved matters to solid phase.
6. Conclusions and Recommendations 6.1 Conclusions This thesis study aimed to investigate the application of organic polymers as coagulants/flocculants to remove the organic micro-pollutants and phosphorous from raw waste water. During the proposed study an inventory was made of the experiences with different polymers with respect to the removal of organic micro pollutants and phosphate. Different polymers were selected and jar tests were performed, testing the different polymers under different conditions: mixing condition, dose, pH. －
2 cationic polymer flocculants (Nalco 71403 and CORE SHELL 71305) and 2 lower dosage coagulant+flocculant combinations (1 anionic combination 8190+7757 and 1 cationic combination 8190+71413) were selected from 5 coagulants and 10 flocculants according to turbidity (suspended solids) removal. These 4 candidates were tested to find the removal mechanism of organic micro-pollutants in waste water.
－
The various mixing conditions for coagulation/flocculation didn‘t affect on the turbidity removal by polymers that much. The relatively optimal mixing conditions for 4 candidates were: Setting
Rapid mixing time(min)
Stirrer velocity 1 (rpm)
G-value 1(s-1)
Slow mixing (min)
Stirrer velocity 2 (rpm)
G-value 2 (s-1)
Settling time (min)
－
Organic micro-pollutants removal mechanisms by coagulation/flocculation It can be concluded that under current conditions polymer do not contribute significantly to remove the pharmaceuticals in both tap water and wastewater. Despite the much better turbidity removal in raw wastewater than filtered wastewater, there is no significant pharmaceutical removal in both matrices. This fact indicated that pharmaceuticals might adsorp on even very fine particles or organic matters that could not be removed by coagulation/flocculation under current polymer dosage and mixing conditions.
－
Turbidity, DOC and Ptot removal In tap water matrix, coagulation/flocculation with polymers could give rise to the formation of only a few and very fine flocs. It resulted in a little turbidity increasing. In suspended solid free waste water (0.45μm filtered wastewater), coagulation/flocculation could result in the formation of fine flocs as well. There were 25~50 NTU turbidity increase (a bit better than tap water), no DOC removal and phosphorous removal. In raw wastewater, larger and settleable flocs were formed which resulted in 65%~70% turbidity removal, 12%~17% Ptot removal, 6%~13% PO 4-P removal and no DOC removal after coagulation/flocculation. The results indicate that polymers worked well on particle removal and phosphorous removals were mainly along with particle removal. The higher turbidity increase by combinations in suspended solids free water indicates that coagulant+flocculant combinations can form flocs from dissolved matters to solid phase.
sufficient contact time that the micro-pollutants need longer time (more than one hour) to attach onto particles. If good relationship can be found between particles removal and micro-pollutants removal in raw wastewater by applying longer contact time or higher dosage, the turbidity removal could be used to select the polymers. If not, the selection principle of polymers still needs to be worked out. Preparation concentration in polymer stock solution In Setting A screening test and Setting B optimal mixing condition test, the concentration in polymer stock solution exceeded the recommended stock solution preparation concentration. It was due to misunderstanding of the polymer information on the Material Safety Data Sheets. For Setting C, D and E, the preparation concentrations were corrected to the right values. Comparing the turbidity removal in 5 settings, it seems that the high preparation concentration don‘t affect on the polymer performance that much. Samples preparation During the elaboration of experimental results, the trickiest part was the calibration of sample results. Since the reliability of analytical results much depends on the sample matrices, the sample preparation procedures were discussed to improve the reliability of pharmaceutical analytical results.
-
To prevent the contamination on the samples, prewash all the materials such as containers, tubes, etc. with demi water.
References [1] Abdessemed, D., Nezzal, G.D. and Ben Aim, R., 2000. Coagulation-adsorptionultrafiltration for wastewater treatment and reuse, Desalination 131, pp. 307-314. [2] Adams, C., Wang, Y., Loftin, K., Meyer, M., 2002. Removal of antibiotics from surface and distilled water in conventional water treatment processes. Journal of Environmental Engineering – ASCE 128 (3), pp. 253 –260. [3] Bhaskar,G.U., Gupta,S.K., 1987. Syntheses and application of anionic polyelectrolytes in water and waste water treatment, WATER AIR SOIL POLLUT. 35(3-4), pp.251-260. [4] Bolto, B., 2007. Organic polyelectrolytes in water treatment, Water research 41, pp. 23012324. [5] Carballa, M., Omil, F., Lema, J.M., 2005. Removal of cosmetic ingredients and pharmaceuticals in sewage primary treatment. Water Research 39, pp. 4790-4796. [6] Chiou,C.T., Peters,L.J., Freed,V.H.,1979. A physical concept of soil –water equilibria for non-ionic organic compounds. Science 206, pp. 831 –832. [7] den Elzen, J.J.M., Malsch,A., 2009. Broninventarisatie Rijnlandse probleemstoffen-Emissie vanuit de AWZI‘s, Hoogheemraadschap van Rijnland, NL. [8] de Ridder, D., 2010. Modeling equilibrium adsorption of organic micropollutants onto activated carbon, Water research 44, pp. 3077-3086. [9] Dignac, M.F., Ginestet, P., Rybacki, D., Bruchet, A., Urbain, V., Scribe, P., 2000. Fate of wastewater organic pollution during activated sludge treatment: Nature of residual organic matter. Water Res 34, pp. 4185 –4194.
[20] Lyman, W.J., Reehl, W.L., Rosenblatt, D.H., 1982. Handbook of Chemical Property Estimation Methods . McGraw-Hill, New York. [21] Mackay, D.M., Roberts, P.V., Cherry, J.A., 1985.Transport of organic contaminants in ground water. Environ.Sci.Technol. 19, pp. 384 –392. [22] Matuszewski, B.K., Constanzer, M.l., Chavez-Eng, C.M., 2003. Anal. Chem 75, pp. 30193030. [23] Moussas, P.A., Zouboulis, A.I., 2009. A new inorganic-organic composite coagulant, consisting of Polyferric Sulphate (PFS) and Polyacrylamide (PAA), Water Research 43, pp.3511-3524. [24] Nozaic, D.J., Freese, S.D., and Thompson, P., 2001. Long term experience in the use of polymeric coagulants at Umgeni Water, Water Sci. Technol.: Water Supply 1 (1), pp. 43 –50. [25] Overzicht analyse en bedrijfsresultaten RWZI‘S, 2010, Hoogheemraadschap van Rijnland, NL. [26] Pinto, M.B., 2008. Effect of coagulant dosing on direct ultrafiltration of municipal wastewater, Master thesis, Universidade Nova de Lisboa. [27] Pollutants in urban waste water and sewage sludge, ICON, 2001. [28] Rebhun, M., Laor, Y., 1998. Using Dissolved Humic Acid To Remove Hydrophobic Contaminants from Water by Complexation- Flocculation Process, Environment Science & Technology 32, pp. 981-986. [29] Rout,D., Verma,R., and Agarwal, S.K., 1999. Polyelectrolyte treatment — an approach for water quality improvement, Water Sci. Technol. 40 (2), pp. 137 –141. [30] Scherrenberg, S.M., Menkveld, H.W.H., Schuurman, D.J., den Elzen, J.J.M. and van der Graaf, J.H.J.M., 2008. Advanced treatment of WWTP effluent; no use or reuse? Water
[41] Thuy,P.T., Moons,K., van Dijk,J.C., Anh,N.V., Van der Bruggen,B., 2008. To what extent are pesticides removed from surface water during coagulation-flocculation? Water and Environment Journal 22 (3), pp. 217 –223. [42] Torres, P., Otth, L., Montefusco, A., Wilson, G., Ramirez, C., Acuna, M., Marin, F., 1997. Infection by intestinal protozoa and helminths in schoolchildren from riverside sectors, with different fecal contamination levels, of Valdivia River, Chile. Bol Chil Parasitol 52, pp. 3-11. [43] van Beelen, E., 2007. Municipal Waste Water Treatment Plant (wwtp) Effluents - a Concise Overview of the Occurrence of Organic Substances, RIWA, NL. [44] van Nieuwenhuijzen, A.F., 2002. Scenario studies into advanced particle removal in the physical-chemical pre-treatment of wastewater, PhD Thesis, DUP, Delft, NL. [45] Vieno,N., Tuhkanen,T., Kronberg,L.,2006. Removalof pharmaceuticals in drinking water treatment: effect of chemical coagulation. Environmental Technology 27(2), pp. 183 –192. [46] Warren, N., Allan, I.J., Carter, J.E., House, W.A., Parker, A., 2003. Pesticides and other micro-organic contaminants in freshwater sedimentary environments – a review, Applied Geochemistry 18, pp. 159-194. [47] Wei, J., Gao,B., Yue,Q., Wang,Y., Li,W., Zhu,X., 2009. Comparison of coagulation behavior and floc structure characteristic of different polyferric-cationic polymer dualcoagulants in humic acid solution, Water Research 43, pp. 724-732. [48] Weishaar, J.L., Aiken, G.R., Bergamaschi, B.A., Fram, M.S., Fujij, R., Mopper, K., 2003. Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon. Environmental Science & Technology 37, pp. 4702 – 4708. [49] Zhang, C., 2009. Removal of dissolved organic matter and phthalic acid esters from landfill leachate through a complexation- flocculation process, Water Management 29,
Appendices Measured concentration of 15 organic micro-pollutants (ng/l) TAP WATER
Atenolol
Bezafibrate
Carbamazepine
FILTERED WASTE WATER
RAW WASTE WATER
Sample name
1
2
Average
Sample name
1
2
Average
Sample name
1
2
Average
T_Non_Spiking
347
347
347
F_Non_Spiking
5343
5920
5631
R_Non_Spiking
3661
4710
4186
T_Spiking
10253
16380
13317
F_Spiking
24595
22448
23521
R_Spiking
18510
21084
19797
T_71403
17244
11881
14562
F_71403
7207
23410
15308
R_no polymer
20919
20640
20780
T_71305
10261
20156
15209
F_71305
24539
24738
24639
R_71403
21703
21924
21813
T_8190+7757
19869
26647
23258
F_8190+7757
25081
22104
23593
R_71305
21297
21274
21285
T_8190+71413
11845
30953
21399
F_8190+71413
24557
18440
21498
R_8190+7757
18532
20822
19677
R_8190+71413
20345
24192
22269
T_Non_Spiking
0
0
0
F_Non_Spiking
179
325
252
R_Non_Spiking
220
528
374
T_Spiking
17245
16242
16743
F_Spiking
15421
18032
16727
R_Spiking
18360
20195
19277
T_71403
15690
15443
15567
F_71403
16952
17771
17362
R_no polymer
19975
20123
20049
T_71305
16230
14940
15585
F_71305
17721
20400
19060
R_71403
19199
19045
19122
T_8190+7757
14553
14625
14589
F_8190+7757
17612
18230
17921
R_71305
18627
19002
18815
T_8190+71413
15092
14540
14816
F_8190+71413
19657
18765
19211
R_8190+7757
18767
19300
19033
R_8190+71413
20142
18421
19281
T_Non_Spiking
131
354
242
F_Non_Spiking
1339
1422
1380
R_Non_Spiking
1018
1434
1226
T_Spiking
9763
15071
12417
F_Spiking
19150
18988
19069
R_Spiking
17990
22416
20203
T_71403
16260
9649
12954
F_71403
21237
19810
20523
R_no polymer
19512
20335
19924
T_71305
9518
15733
12625
F_71305
21728
20788
21258
R_71403
21352
18962
20157
T_8190+7757
18027
21493
19760
F_8190+7757
22582
19007
20795
R_71305
18878
18168
18523
T_8190+71413
11075
24860
17968
F_8190+71413
21583
18920
20252
R_8190+7757
16873
19159
18016
R_8190+71413
18706
19381
19043
52
TAP WATER
Clofibric acid
Diclofenac
Gemfibrozil
Ibuprofen *
FILTERED WASTE WATER
RAW WASTE WATER
Sample name
1
2
Average
Sample name
1
2
Average
Sample name
1
2
Average
T_Non_Spiking
0
0
0
F_Non_Spiking
5401
8284
6842
R_Non_Spiking
6054
3815
4935
T_Spiking
13627
13488
13558
F_Spiking
20424
24080
22252
R_Spiking
18818
24853
21835
T_71403
16181
17813
16997
F_71403
13572
22206
17889
R_no polymer
21891
20736
21314
T_71305
17663
16164
16914
F_71305
23885
28554
26220
R_71403
17742
19466
18604
T_8190+7757
8128
13964
11046
F_8190+7757
22183
21734
21958
R_71305
17343
16717
17030
T_8190+71413
8622
14272
11447
F_8190+71413
22392
20567
21479
R_8190+7757
23054
17793
20423
R_8190+71413
18228
18314
18271
T_Non_Spiking
0
0
0
F_Non_Spiking
0
0
0
R_Non_Spiking
0
0
0
T_Spiking
21019
18904
19962
F_Spiking
12905
17011
14958
R_Spiking
17535
26327
21931
T_71403
18141
27238
22690
F_71403
21370
20417
20893
R_no polymer
19330
11219
15275
T_71305
27384
28423
27904
F_71305
17794
14049
15921
R_71403
12037
20391
16214
T_8190+7757
19922
22637
21279
F_8190+7757
12823
21011
16917
R_71305
22218
25513
23865
T_8190+71413
22864
11510
17187
F_8190+71413
21563
17899
19731
R_8190+7757
25624
14420
20022
R_8190+71413
22597
28595
25596
T_Non_Spiking
0
3528
1764
F_Non_Spiking
5642
4426
5034
R_Non_Spiking
3810
3516
3663
T_Spiking
27505
26005
26755
F_Spiking
23827
41311
32569
R_Spiking
27271
39972
33621
T_71403
24369
22092
23230
F_71403
25969
27836
26903
R_no polymer
34323
32553
33438
T_71305
25028
25598
25313
F_71305
28580
30438
29509
R_71403
36094
31789
33941
T_8190+7757
23030
23915
23473
F_8190+7757
32034
27647
29840
R_71305
28289
28826
28558
T_8190+71413
21942
22349
22145
F_8190+71413
30865
31968
31416
R_8190+7757
32659
28733
30696
R_8190+71413
30613
32451
31532
T_Non_Spiking
0
0
0
F_Non_Spiking
19477
12826
16151
R_Non_Spiking
15403
12303
13853
T_Spiking
21815
15534
18674
F_Spiking
32666
40248
36457
R_Spiking
26256
41966
34111
T_71403
18982
16132
17557
F_71403
29121
31286
30204
R_no polymer
22189
31413
26801
53
TAP WATER
Ketoprofen
Metformin
Metoprolol
Naproxen
FILTERED WASTE WATER
RAW WASTE WATER
Sample name
1
2
Average
Sample name
1
2
Average
Sample name
1
2
Average
T_71305
14494
28778
21636
F_71305
22450
34263
28356
R_71403
31903
22647
27275
T_8190+7757
17889
18285
18087
F_8190+7757
31254
33974
32614
R_71305
33849
17435
25642
T_8190+71413
24354
19525
21939
F_8190+71413
33523
44066
38795
R_8190+7757
23151
29452
26302
R_8190+71413
28721
29230
28976
T_Non_Spiking
46
0
23
F_Non_Spiking
390
585
487
R_Non_Spiking
93
148
121
T_Spiking
14518
18031
16274
F_Spiking
14224
10310
12267
R_Spiking
11692
14394
13043
T_71403
15923
16326
16125
F_71403
13589
14022
13805
R_no polymer
15356
12918
14137
T_71305
13460
16755
15107
F_71305
13960
15735
14847
R_71403
15514
18804
17159
T_8190+7757
15087
16346
15716
F_8190+7757
14643
14890
14767
R_71305
14719
18170
16444
T_8190+71413
13419
17205
15312
F_8190+71413
16058
14716
15387
R_8190+7757
18375
18592
18484
R_8190+71413
15688
18221
16954
T_Non_Spiking
203
186
194
F_Non_Spiking
20402
21222
20812
R_Non_Spiking
15314
16929
16122
T_Spiking
25135
23613
24374
F_Spiking
18650
19719
19185
R_Spiking
19477
20507
19992
T_71403
19218
18681
18949
F_71403
14652
22537
18595
R_no polymer
19327
19653
19490
T_71305
21240
17996
19618
F_71305
19295
21521
20408
R_71403
23976
25440
24708
T_8190+7757
16948
17484
17216
F_8190+7757
21538
22208
21873
R_71305
23333
24497
23915
T_8190+71413
17518
23050
20284
F_8190+71413
21284
19256
20270
R_8190+7757
25260
24931
25095
R_8190+71413
23129
20306
21718
T_Non_Spiking
365
398
382
F_Non_Spiking
5463
5864
5664
R_Non_Spiking
3573
4718
4146
T_Spiking
10332
16008
13170
F_Spiking
24231
22031
23131
R_Spiking
18539
20787
19663
T_71403
16795
11868
14332
F_71403
7365
22545
14955
R_no polymer
20490
20113
20302
T_71305
10029
19162
14596
F_71305
23622
24186
23904
R_71403
21404
21123
21264
T_8190+7757
18328
26298
22313
F_8190+7757
24012
21462
22737
R_71305
21152
20650
20901
T_8190+71413
11492
30465
20978
F_8190+71413
24846
17611
21228
R_8190+7757
17836
20587
19211
R_8190+71413
20548
24657
22602
R_Non_Spiking
4619
4647
4633
T_Non_Spiking
162
190
176
F_Non_Spiking
4694
4789
4741
54
TAP WATER
Paracetamol *
Propranolol *
Sulfamethoxazole
FILTERED WASTE WATER
RAW WASTE WATER
Sample name
1
2
Average
Sample name
1
2
Average
Sample name
1
2
Average
T_Spiking
15618
12554
14086
F_Spiking
13109
16640
14875
R_Spiking
18188
21534
19861
T_71403
14220
14770
14495
F_71403
13565
18939
16252
R_no polymer
19868
20405
20136
T_71305
14696
14877
14786
F_71305
13922
20717
17319
R_71403
20550
20733
20642
T_8190+7757
11479
14520
13000
F_8190+7757
15267
19993
17630
R_71305
19149
18507
18828
T_8190+71413
11546
14694
13120
F_8190+71413
16281
18604
17442
R_8190+7757
19320
18785
19053
R_8190+71413
20000
19758
19879
T_Non_Spiking
1
16
9
F_Non_Spiking
36998
36021
36510
R_Non_Spiking
20144
29027
24586
T_Spiking
9787
17067
13427
F_Spiking
36997
36159
36578
R_Spiking
27496
26379
26938
T_71403
16744
12371
14557
F_71403
35436
33678
34557
R_no polymer
38478
50268
44373
T_71305
9724
20043
14884
F_71305
34336
34264
34300
R_71403
19928
16129
18029
T_8190+7757
18676
28893
23784
F_8190+7757
36896
35706
36301
R_71305
17831
20875
19353
T_8190+71413
11864
33401
22632
F_8190+71413
39118
42071
40594
R_8190+7757
29994
13784
21889
R_8190+71413
35791
395150
215470
T_Non_Spiking
0
0
0
F_Non_Spiking
626
1173
899
R_Non_Spiking
266
697
481
T_Spiking
63185
73849
68517
F_Spiking
132800
119699
126250
R_Spiking
63559
70848
67204
T_71403
104334
72956
88645
F_71403
118915
155954
137435
R_no polymer
66929
74241
70585
T_71305
72093
102234
87164
F_71305
163235
134036
148636
R_71403
88597
70640
79618
T_8190+7757
138886
162339
150613
F_8190+7757
152317
73967
113142
R_71305
68292
62320
65306
T_8190+71413
84703
178761
131732
F_8190+71413
122125
68339
95232
R_8190+7757
53347
71618
62483
R_8190+71413
61101
130587
95844
T_Non_Spiking
66
65
65
F_Non_Spiking
289
310
299
R_Non_Spiking
490
481
485
T_Spiking
20831
19065
19948
F_Spiking
14379
16450
15415
R_Spiking
16173
17882
17028
T_71403
18832
18261
18547
F_71403
13921
15752
14837
R_no polymer
17094
17877
17486
T_71305
19642
18031
18836
F_71305
15068
18093
16580
R_71403
16682
17513
17098
T_8190+7757
17551
17858
17705
F_8190+7757
16426
16399
16413
R_71305
16302
17260
16781
T_8190+71413
18209
18074
18141
F_8190+71413
17617
16071
16844
R_8190+7757
16806
17874
17340
55
