Accepted Manuscript

Title: Drinking water sludge of Moroccan capital: statistical

analysis of environmental aspects

Author: Mohammed Dahhou Mohammed El Moussaouiti

Mohammed El Morhit Said Gamouh Souad Moustahsine

PII: S1658-3655(16)30070-X
DOI: http://dx.doi.org/doi:10.1016/j.jtusci.2016.09.003
Reference: JTUSCI 330

To appear in:

Received date: 21-5-2016

Revised date: 3-9-2016
Accepted date: 11-9-2016

Please cite this article as: M. Dahhou, M.E. Moussaouiti, M.E. Morhit, S.
Gamouh, S. Moustahsine, Drinking water sludge of Moroccan capital: statistical
analysis of environmental aspects, Journal of Taibah University for Science (2016),
http://dx.doi.org/10.1016/j.jtusci.2016.09.003

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 1 Drinking water sludge of Moroccan capital: statistical
2 analysis of environmental aspects

3 Mohammed Dahhoua,*, Mohammed El Moussaouiti a,*, Mohammed El Morhitb,

4 Said Gamouhc, Souad Moustahsined

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a
6 Laboratory of Materials, Nanotechnology and Environment, Department of Chemistry,

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7 Faculty of Science, Mohammed V University Rabat, 1014, Morocco.
b

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8 Laboratory of Microbiology, Research Team Health, Water and Environment. Faculty of
9 Medicine and Pharmacy. University Mohammed-V, Rabat, Morocco.
c

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10 LIMAT Laboratory, Department of Chemistry, Faculty of Science Ben M’Sik, Hassan II
11 University Casablanca, Morocco.
d
12 The National Office of Electricity and Drinking Water, Rabat, Morocco.
13
14 *Corresponding author, Phone/Fax: +212 537 77 54 404
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15 E-mail address: [email protected] (Mohammed Dahhou).
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16 E-mail address: [email protected] (Mohammed El Moussaouiti).
17
18
19 Abstract This paper reports a study on the evaluation of metal pollution degree, trace
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20 elements, and the seasonal evolution of various physico-chemical parameters of Moroccan

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21 drinking water sludge by statistical approach. The physico-chemical parameters of liquid raw
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22 sludge (water temperature (Tw), volatile suspended solids (VSS), suspended matter (SM)),
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23 Conductivity (Cond(s) and pH(s)), and heavy metals/trace elements in dried hydroxide sludge

24 (Pb, Cr, Cd, Fe, Al, Cu, Zn, P, N, K, C and pH), along with supernatant (Cd(s), Pb(s), Cr(s))
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25 were analyzed by principle component analysis (PCA). The contents of Cd and Cr in

26 supernatant did not exceed the recommended limits of trace elements in the treated

27 wastewater for irrigation. However, the contents of Zn, Pb and Cu in dried hydroxides sludge

28 exceeded the limits defined by the international standards. Principle component F1 explicates

29 that 25.20% of the variance is mainly due to Zn and conductivity, while the principle

30 component F2 reveals that 21.00% of the variance appears because of the presence of

31 identified physico-chemical parameters and particularly C and pH(s). Certain merits of the

Page 1 of 20
 1 present approach are pointed out, and its important applications on solving crucial

2 environmental issues are discussed.

3 Keywords: Drinking water sludge; physico-chemical parameters; heavy metals; trace

4 elements; statistical analysis.

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5

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6 1. Introduction

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7 Pollution from heavy metals is among the serious environmental issues that accompany the

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8 rapid economic development globally [1]. Pollution from heavy metals in aquatic systems, for

10
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instance, has become a threat and has great potential for creating environmental risks to

human health which may affect the ecological food chain as these metals are not
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11 biodegradable [1, 2]. Industrial processes generate waste which is mostly released into the

12 environment. Industrial activities, including treatment plants or purification of water

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13 according to their employed treatments generate large amounts of material and organic
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14 pollutants, including heavy metals by absorption of the latter by the sludge which clearly
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15 becomes a reservoir of heavy metals [2, 3].

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16 Drinking water treatment plants generate hydroxide sludge through the filters and sludge

17 blanket decanters [3-5]. Clarification allows the removal of suspended matter (SM) and
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18 colloids and is generally divided into three successive operations: coagulation, flocculation

19 and sedimentation. The common characteristic of all kinds of sludges is to create a highly wet

20 waste with liquids of insignificant value [6]. The hydroxide sludge has a very similar

21 constitution, differs only in the suspended matter concentration. Sludge settling ponds include

22 most of the suspended solids in the raw water and the metal hydroxide produced by

23 coagulation [3, 4, 7, 8]. They may also contain a low CaO contents from a clay of low

24 limestone, as already been seen in the sludge of Bouregreg drinking water production unit.

Page 2 of 20
 1 The washing water filters contain essentially the same residues as those found in the sludge

2 settling tanks, though in the much lower concentrations [3, 9].

3 Heavy metals are one of the most ancient and severe water pollutants. They can be present

4 in sludge in variable concentrations depending on the origin of the sludge (industrial or

5 residential), which remains a major obstacle in sludge valorization. Metals in sludge are

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6 typically available in soluble, exchangeable and adsorbed forms, associated mainly with

7 organic matter, bound to carbonates and sulfides in crystalline residues. The presence of

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8 complexing agents, the precipitating ligands and concentration of some physico-chemical

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9 parameters such as pH, the temperature and the redox potential can therefore influence the

10 heavy metals in sludge [10-12]. Nevertheless, the heavy metals present in the sludge need

11
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rigorous and stringent assessment with respect to their relative concentrations in sludge, for

12 eventual and effective desired applications.

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13 In the mentioned context, the aim of our present work is to carry out a detailed quantitative

14 analysis primarily of the distribution of heavy metals in dried sludge and supernatant of the
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15 drinking water treatment plant of Bouregreg (Rabat, Morocco), as well as the trace elements
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16 and the physico-chemical parameters affecting raw sludge, by employing statistical approach.

17 The obtained results will be interpreted and discussed with particular regard to valorization of
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18 the sludge under consideration, for potential applications.

19
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20 2. Materials and methods

21 Drinking water of the Bouregreg processing station is the result of a pre-treatment which

22 consists of a screening and disinfection or peroxidation by adding chlorine gas (Pre-

23 chlorination). Aluminum sulfate Al2(SO4)3 is the most used coagulant by this station along

24 with the polyelectrolyte or alginate as flocculants. Decantation is primarily carried out in the

Page 3 of 20
 1 decanter sludge bed. Then, the filtration is conducted through pools including the sand layer

2 and washing of filters is done by reversing the direction of flow of water.

3 2.1. Characterization

4 Liquid raw drinking water sludge has been collected on monthly basis for a period of one

5 year from drinking water decantation plant of the drinking water treatment plant of Bouregreg

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6 (Rabat-Morocco). The raw sludge collected samples underwent a settling period of two hours

to recover the supernatant and the corresponding sludge hydroxides. The supernatant was

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7

8 stored at 4 °C, and the dried sludge is recovered in the open air for 8 days. Different physico-

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9 chemical parameters were determined using the following techniques.

10 The pH measurement is performed after ten minutes of homogenization on the liquid

11
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portion by using a pH-meter type of mark W.T.W. [13]. The Conductivity (Cond(s)) of

supernatant is measured by Conductometer of the type W.T.W Mark. The filtrate of the
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12

13 sample is filtered under vacuum using a filter glass micro-fiber and the residue is dried at 105
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14 °C and weighed again. The mass difference corresponds to the content in SM in the sample
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15 volume filtering. The quantity of VSS is obtained by the difference between the weight of the
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16 ash residue at 550 °C and dried at 105 °C [14].

17 The elementary analysis (for the detection of C, H, N, S, O) by employing Flash

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18 Thermoanalyzer EA 112, is carried out on the total combustion of the analytical sampling at
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19 1050 °C under a stream of oxygen and pressure. The products are separated on a

20 chromatographic column and measured by a thermal conductivity detector.

21 The analysis of heavy metals is carried by the atomic emission spectrometer of type ICP-

22 AES and brand Ultima 2 Jobin Yvon (spectral range 120-800 nm) after dilution and

23 acidification, in view of making the metals soluble in the dried hydroxide sludge.

24 2.2. Statistical treatment

Page 4 of 20
 1 Principal components analysis (PCA) is the most common technique used to summarize

2 patterns among the variables in multivariate datasets. The PCA is a way of identifying

3 patterns in variables, and expressing data in such a way to highlight their similarities and

4 differences. The main advantage of PCA is that, once the patterns have been found, data can

5 be compressed reducing the number of dimensions, without much loss of information [15,

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6 16].

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7 In order to interpret the analytical data of the analyzed elements and extrapolate the

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8 resulting pollution-related information of hydroxide sludge generated by the drinking water

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9 treatment plant of Bouregreg, the method of the Principal Component Analysis (PCA) was

10 used whose application in the field of environmental studies has been the subject of various

11 an
studies [17-19]. The physico-chemical parameters of liquid raw sludge (water temperature

12 (Tw), volatile suspended solids (VSS), suspended matter (SM)), and heavy metals/trace
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13 elements in dried hydroxide sludge (Pb, Cr, Cd, Fe, Al, Cu, Zn, P, N, K, C and pH), along

14 with supernatant (Cd(s), Pb(s), Cr(s), Conductivity (Cond(s)) and pH(s)), were studied by
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15 principle component analysis (PCA)

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16
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17 3. Results and discussion

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18 3.1. Analysis of spatiotemporal rating parameters

19 The result of physicochemical analysis by spatiotemporal rating parameters of liquid raw

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20 sludge, dried hydroxide sludge, and supernatant are represented in Table 1. Besides, results

21 associated with the heavy metals and trace elements in sludge hydroxides and supernatant are

22 represented in Table 2.

23 3.1.1. Air temperature (Ta) and water temperature (Tw)

24 The maximum temperature (20 °C) was recorded during the warm season (August 2011)

25 and the minimum (11 °C) was obtained during the cold season (January 2012). This reflects

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 1 the influence of the regional climate. The water temperature is considered moderate between

2 14 °C and 19 °C. The different temperatures are controlled below 30 °C which is regarded as

3 the limiting value of direct discharge into the receiving environment. Likewise, the values less

4 than 35 °C are considered as an indicative limits for irrigation water [20].

5 The water temperature (Tw = 11 °C) showed high value in comparison with air

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6 temperature (Tw = 16 °C), indeed due to currentology runoff and torrential rain of the winter

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7 season.

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8

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9 3.1.2. pH dried hydroxide Sludge (pH) and pH Supernatant (pH(s))

10 The pH measurement reflects the H3O+ ion concentration. According to Gagnard et al.

11
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[21], we can classify the Supernatant and dried hydroxide sludge as follows:

12 - The pH of supernatant (pH(s)) is slightly alkaline (7.2-7.5) during the period of the
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13 summer, autumn and winter, and alkaline (7.5-8.7) during the spring season. According to the

14 WHO [22], the pH of drinking water must be between 6.5 and 8.5.
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15 - The pH of dried hydroxide sludge (pH) is close to neutral (6.8-7.2) except during the
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16 month of November and April, in which, we found that the pH is slightly alkaline (7.2-7.5).

17 Our results showed that Bouregreg dried hydroxides sludge are slightly alkaline. The pH of
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18 dried hydroxide sludge recorded is between 6.8 and 7.3, caused by the step of coagulation-

19 flocculation of water by salt of strong acid such as aluminum sulphate, which causes
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20 precipitation of heavy metals and their adsorption by the sludge. The value of pH less than 5

21 or greater than 8.5 affects the growth of microorganisms.

22
23 3.1.3. Conductivity of the supernatant (Cond(s))

24 The recorded values of the supernatant conductivity ranged from 540 µs/cm in February

25 2012 and 766µs/cm (Table 1) in June of the same year. These values have not exceeded the

Page 6 of 20
 1 maximum conductivity value for drinking water (1055 µs/cm). Similarly, these average values

2 are less than 2700 µs/cm, considered direct discharge limit value in the receiving environment

3 [23]. These supernatant are characterized by average values between 666 µs/cm and 1000

4 µs/cm, indicating a strong mineralization of supernatant [24].

5
6 3.1.4. SM and VSS of liquid raw sludge

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7 Sludge used in the present study, is characterized by a mean SM concentration of 39 g/L,

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8 with a minimum concentration of 6.7 g/L and a maximum concentration of 100.7 g/L.

9 Moroccan rejection standard in this case is 50 mg/l [20]. The high VSS load was recorded

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10 during the summer and autumn seasons is probably due to a sharp hydrological event (flood)

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12
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in the Sidi Mohammed ben Abdallah dam. But the load SM can be attributed to intense

erosion of the watershed, following sudden rainstorms that cause an increase in SM.
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13 The moisture rate is an important parameter in selecting the treatment procedure. A

14 reported experience in the literature with the supercritical water gasification (SCWG) of
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15 biomass with moisture contents ranging from 76.2 to 94.4 wt% suggests that as the moisture
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16 contents decrease, the total gas yield decreases as well with a significant reduction in CO2
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17 yield and slight reduction in H2 and CH4 yields. It has been proven that carbonization process
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18 is accelerated in lower moisture contents and thus the obvious reduction of CO2 yield can be

19 attributed to the carbon transformation into coke therein [25].

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20 The VSS/SM report elucidates the organic nature of the sludge. The Means of VSS/SM

21 vary from 20.3 to 35% (Table 1), which corresponds to the percentage of sludge in which the

22 mineral material is high. However, this ratio VSS/MS is between 50% and 75%, for high

23 organic sludge [26].

24
25 3.2. Evaluation of heavy metals and trace element in dried hydroxide sludge and supernatant

Page 7 of 20
 1 The results estimate of the higher concentrations of Cd, Pb and Cr in the dried hydroxide

2 sludge and supernatant. The obtained results show the concentrations of Cd, Pb and Cr in all

3 the samples of sludge and their supernatant of the Drinking water treatment plant of

4 Bouregreg, establish descending order for the supernatant: [Crs] > [Pbs] > [Cds] and for [C] >

5 [P] > [N] > [Al] > [Fe] > [K] >[Zn] > [Cu] > [Pb] > [Cr] > [Cd] for the dried hydroxide sludge

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6 (Table 2). Their mean values in dried hydroxide sludge are significantly higher than those

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7 found in the supernatant. The metal contents in the supernatant ranged from 0.003-0.042 mg/l

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8 cadmium, 0.003-0.079 mg/l lead, and 0.082-0.051 mg/l chromium (Table 2). These mean

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9 values are lower than those obtained by the recommended limits of trace elements in the

10 treated wastewater for irrigation (Table 3) [27].

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To the best of our knowledge, no regulation exists hitherto regarding the pollutant loads

12 contained by the drinking water sludge of production unit. However, the thresholds suggested
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13 by the French standard [28] can be used as reference as shown in Table 4. These mean values

14 are compared with the highest concentrations of French standards in the sludge giving very
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15 low cadmium and chromium concentrations which do not reflect pollution. As far copper,
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16 lead and zinc in the dried hydroxide sludge are concerned, they show higher values than the
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17 reference values of the French standards, emphasizing moderate pollution by these metals.
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18 According to Schmill et al. [29], concentrations of Cu and Zn in sludge pose a major problem

19 in the case of cement industry.

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20 The high concentration of iron can be related to the structure of the silicates which are

21 among the major constituents of dried hydroxide sludge [30]. The presence of iron in sludge

22 can promote the proliferation of certain strains of bacteria that precipitate in corroded iron

23 pipes [31].

24 Phosphorous can be found in nature in various oxidized forms say, meta HPO3, ortho

25 H3PO4 and pyro H4P2O7. In aqueous medium, meta and pyro forms tend towards the ortho

Page 8 of 20
 1 form. Between pH 5-8, the phosphorous exists considerably in the form of ortho phosphate

2 [32, 33]. Their presence in natural waters is associated with the characteristics of the land and

3 the decomposition of organic matter phosphate. Excess phosphorus can potentially be

4 hazardous in water. Indeed, high levels of PO4-3 lead to the eutrophication phenomenon which

5 results in an increase of algae in tanks and large pipes. They may therefore severely influence

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6 on the passage of light, oxygen consumption, etc. in tanks which may eventually cause in

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7 serious wildlife risks [34].

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8
9 3.3. Typology of variables studied in water of the drinking water treatment plant of Bouregreg

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10 A significant correlation exists among different physico-chemical parameters, trace

11

12
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elements and heavy metals of liquid raw sludge, supernatant and dried hydroxide sludge

(Table 5). Indeed, the obtained results show that in the dried hydroxide sludge, Cu and N
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13 correlate in a significant way with high correlation coefficient estimated to 0.722. However,

14 Cu and Zn noted a low correlation with r = 0.545.

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15 In addition, the conductivity of the supernatant (Cond(s)) showed a strong correlation with
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16 metals including Cd(s) (r =- 0.725), and Pb(s) (r = -0.503) present in the supernatant, as well
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17 as with Cr (r = -0.644), Fe (r = 0.620), Cu (r = 0.583) and Zn (r = 0.706) in the dried

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18 hydroxide sludge. This reflects a major influence of these metals on these parameters, which

19 are the dependent variable. Moreover, measurement of the conductivity parameter is a good
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20 assessment of the degree of mineralization of water in which each ion is conductivity specific

21 [35].

22 The coefficient of correlation between the conductivity of the supernatant and parameters

23 such as pH(s) and temperature remain low (r = -0.02 and r = 0.05, respectively, indicating

24 eventual non-involvement of these parameters in determining the electrical conductivity of the

25 water. Values of pH(s) of supernatant are positively correlated with Fe in dried hydroxide

Page 9 of 20
 1 sludge (r = 0.529). This observation allows noticing the influence of this parameter on the Fe

2 distribution in the dried hydroxide sludge.

3 The temperature plays a very important role in the solubility of the salts and especially

4 gases and the determination of the pH [16]. In our study, the water temperature (Tw) sowed a

5 moderate positive correlation with the carbon in the dried hydroxide sludge (r = 0.637),

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6 suggesting that the biological factor causes influences on the carbon contents and plays a role

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7 in its distribution.

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8 Fe is moderately correlated with Al (r =- 0.46) in dried hydroxide sludge which might be

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9 explained on the basis of the preference of these metals about other silicates and oxy-

10 hydroxide in comparison with Fe and Al. In dried hydroxide sludge, a positive correlation was

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noted between N and Pb. Indeed, this correlation (r = 0.630) was moderately significant.

12 However, a low correlation (r = -0.291) was recorded between N and Pb(s); this situation is
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13 due to higher accumulation of N in sludge.

14 In addition, the correlation coefficient between the calculated contents of Cd and Cr in

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15 hydroxides sludge is significant (r = 0.815) indicating a strong affinity between these

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16 elements, suggesting also a common origin of the two metals. Cd(s) behaves in a relatively
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17 similar way as Pb(s) in supernatant. The correlation coefficient between these metals was r =
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18 0.59, which could be attributed to its higher chemical affinity in the sludge.

19 Suspended matter (SM) of raw sludge correlates significantly with very volatile suspended
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20 solids (VSS) with r = 0.997. SM and VSS have significant correlations with lead and nitrogen

21 in dried sludge. These elements were accumulated with organic particles in suspended and

22 dissolved forms. Lead and nitrogen are trapped in the particles that settle to bottom.

23 PCA allows a treatment of all the water data collected associated with the drinking water

24 treatment plant of Bouregreg and describes the structure by two main gradients F1 and F2. It

25 was conducted on a data matrix consisting of 12 samples (1 station x 12 campaigns) during

Page 10 of 20
 1 which the 21 variables (Cd(s), Pb(s), Cr(s), Cd, Pb, Cr, Fe, Al, Cu, Zn, P, N, K, C, pH(s), pH,

2 Tw, Ta, Cond(s), SM and VSS) were analyzed. The values of the two components F1 and F2

3 and their contribution to the total inertia are presented in Fig. 1A.

4 The results (Fig. 1A) can perform an initial typological approach of the different variables

5 according to their affinities and their combinations on the first two principal components from

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6 their contribution. The F1 and F2 axes determine 46.20 % of the total information (25.20 %

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7 for axis F1 and 21.00 % for axis F2). The values of the PCA, the circle of correlation and

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8 factorial maps and the campaigns are shown in Fig. 1B and C.

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9 Axis F1 is determined by Zn (r = 0.83) and conductivity (r = 0.82). It defines a gradient of

10 mineralization opposite to the contamination gradient in Pb (r = -0.742) and Cd (r = 0.741)

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reflecting the anthropic origin. This result disagrees with that found in previous studies

12 showing that increasing conductivity keeps the Pb at high values in sludge unlike its water
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13 values where it is much more soluble. And for Pb it could be due to the exhaust gas of the

14 vehicles [36]. This state promotes its release in water. El Morhit et al. [41] explained this
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15 situation by remobilization and release of the heavy metals.

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16 For Zn, that it is in contrary with Pb, its presence in dried hydroxide sludge is favored by
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17 low mineralization of the water and by strong agricultural activity. The same phenomenon
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18 was explained by previous studies [37] Increasing conductivity promotes its release in

19 supernatant.
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20 Axis F2 is represented by pH(s) (r = 0.81) and C (r = 0.59) (Fig. 1B). It defines a carbon

21 gradient opposite the contamination gradient in suspended matter (r = 0.81) and volatile

22 matter (r = 0.82) due the natural origin. Indeed, this is characterized by the presence of the

23 ferro-magnesium related to the geological context of the area. However, the influence of

24 seasonality, particularly temperature, seems less noticeable. No relationship emerged between

25 this parameter and the content of conductivity. The water of the drinking water treatment plant

10

Page 11 of 20
 1 of Bouregreg showed that a pH (s) varies in relation to carbon fluctuations of the organic

2 matter.

3 The global analysis is used to define a typology dominated by individualization of three

4 campaigns groups GI, GII and GIII (Fig. 1C). This spatial organization releases the exact

5 location of campaigns relative to their situation:

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6 GI: it combines two periods (July-11 and Aug-11) which have Zn and Cu pollution, whose

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7 waters are mediocre to poor.

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8 GII: it contains the five periods (Nov-11, Oct-11, Sept-11, Mar-12 and May-12), which

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9 also has poor water contamination quality but relatively less contaminated compared with that

10 of the G1 and GIII groups. This difference between the contamination of the water produced

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by these two groups could certainly be explained by the existence of wastewater due to the

12 strong activity during these periods in the drinking water treatment plant of Bouregreg.
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13 GIII: It isolates the study time (Dec-11, Feb-12 and Jan-12) which has contaminated water

14 of very poor quality, characterized by a very high concentration of Cd (s) and Pb (s) pollution.
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15 The maximum values of Cd and Pb were recorded at high significant during the winter
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16 season. This confirms the origin of a domestic wastewater from the Rabat region. However,
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17 significantly higher values of conductivity and Zn were reported during the summer season.
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18 In previous study, the deposition rates of Cd were significantly higher in summer and

19 winter as compared to rainy season, however, Pb deposition rate was significantly higher in
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20 rainy and summer seasons as compared to winter season [38]. But in another study,

21 significantly elevated average levels of the metals (except Cd and Cr) are noticed during

22 summer compared with winter. It could be due to the leaching of the metals into the reservoir

23 from the roadside and agricultural runoffs during wet summer season [39].
24
25 4. Conclusion

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Page 12 of 20
 1 This study highlights an important impact of drinking water sludge production unit on the

2 environment. The sludge produced is a reservoir of heavy metals, where the heavy metals can

3 be trained by the rainwater and contaminate soils and nearby streams. Principle component

4 analysis (PCA) statistical tool is employed to asses the extent of pollution caused by heavy

5 metals, and to analyze the various physico-chemical parameters. PCA confirms the existence

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6 of a significant correlation between Cu, N and Zn; VSS and SM; N, and Pb; C and Tw;

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7 Cond(s), Cd(s), Pb(s), Cr, Fe, Cu, Zn and pH(s); pH(s) and Fe; N and Pb; Cd and Cr; and

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8 Cd(s) and Pb(s). The existence of a significant correlation between Cd and Cr hydroxides in

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9 the sludge shows that there is a high chemical affinity between these two metals in the

10 hydroxide sludge. SM and VSS have significant correlation with lead and nitrogen hydroxide

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sludge which suggests that these metals are brought by particles suspended and dissolved

12 organic matters and the minerals. These concentrations can be explained by the deposition and
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13 the gradual accumulation of these metals in the dry hydroxide sludge. The accumulation of

14 heavy metals in hydroxide sludge is often made by adsorption and/or precipitation. Thus, this
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15 study contributes in understanding the possible causes of environmental pollution, and guides
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16 to certain probable ways of controlling it. In addition, the constituents present in the studied
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17 sludge can potentially be the raw materials for cement after appropriate thermal treatment, as
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18 already been elaborated in our previous study [3,4,40].

19
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20 References
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22
23 [1] Z. Zhou, T. Huang, Y. Li, W. Ma, S. Zhou, S. Long, Sediment pollution characteristics

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15 [8] S. Ishikawa, N. Ueda, Y. Okumura,Y. lida, K. Baba, Recovery of coagulant from water
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2 novel approach of immobilized modified sludge biomass based adsorbents, Sep. Purif.

3 Technol. 163 (2016) 215-227.

4 [12] R. Shahabaldin, P. Mohanadoss, T. Amirreza, M. Shaza-Eva, M.D. Mohd-Fadhil, T.

5 Shazwin-Mat, S. Farzaneh, S. Fadzlin-Md, Perspectives of phytoremediation using

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6 water hyacinth for removal of heavy metals, organic and inorganic pollutants in

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7 wastewater, J. Environ. Manage. 163 (2015) 125-133.

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http://www.ceaeq.gouv.qc.ca/methodes/chimie_inorg.htm

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16 [15] S. Sivakumar, A. Chandrasekaran, R. Ravisankar, S.M. Ravikumar, J. Prince Prakash

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23 Loukkos estuary (Atlantic Coast, Morocco), Bull. Sci. Inst., Earth Sci. Sec. 30 (2008)

24 39-47.

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6 characterizing the water quality of the estuary Loukkos (Morocco), Bull. Sci. Inst.,

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15 drinking water treatment sludges as raw materials to produce concrete and mortar. Am.
e

16 J. Environ. Sci. 4 (2008) 223-228.

pt

17
ce

18 Table 1 Study of Physico-Chemical Parameters in sludge hydroxides and supernatant

19
Sr. No. pH(s) pH Tw (°C) Ta (°C) Cond(s) (µs/Cm) SM (g/L) VSS (g/L) VSS/SM (%)
Ac

JuL-11 7.4 6.8 16 20 750 39.9 13.5 33.8

Aug-11 7.3 7.1 17 20 755 100.3 35.1 35.1
Sep-11 7.4 7.1 17 20 671 66.8 20.3 30.3
Oct-11 7.4 7. 17 19 677 100.7 20.3 35.2
Nov-11 7.6 6.8 17 18 657 40.8 14.3 35
Dec-11 7.4 7 16 17 640 67.3 20.9 31.1
Jan-12 7.4 7.1 16 11 650 8.8 2.7 30.4
Feb-12 7.4 7.2 16 20 540 8.5 2.4 28.6
Mar-12 7.7 7.2 14 16 707 6.7 2.0 29.7
Apr-12 7.8 7.3 14 15 726 10.1 2.5 25.1
May12 7.7 7.1 16 19 682 10.2 2.1 20.3
Jun-12 7.8 7.2 19 18.5 766 7.9 1.7 21.4
Average 7.5 7.1 16.3 17.8 685.1 39.0 12.7 29.6
Standard deviation 0.2 0.2 1.4 2.7 62.7 36.5 12.8 5.1

17

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 1 Table 2 Studied of heavy metals and nutrients in sludge hydroxides and supernatant.
2
Sr. No. Concentration of heavy metals in the Concentration of heavy metals and nutrients in dried hydroxide sludge
supernatant
Cd(s) Pb(s) Cr(s) Cd Pb Cr Cu Zn Al Fe P N K C
(10-3mg/l) (10-3mg/l) (10-3mg/l) (mg/Kg) (mg/Kg) (mg/Kg) (103mg/Kg) (103mg/Kg) (%) (%) (%) (%) (%) (%)

JuL-11 4 20 51 0.3 103.3 8 1.69 3.57 3.3 1.6 6.3 4.1 0.6 18
Aug-11 5 21 52 0.4 111 8.1 1.6 3.7 3 1.7 6.4 4.4 0.5 16.6
Sep-11 4 51 57 0.3 98.2 10 1.34 3.15 3.1 1.9 6.8 4 0.6 15.7
Oct-11 15 45 82 1 84.1 18 1.45 2.79 2.5 1.5 6.3 3.9 0.5 15
Nov-11 22 48 76 01 93.2 21.5 1.37 2.9 2.8 1.6 6.6 3.7 0.1 14.7
Dec-11 9 31 73 0.8 90.5 18.4 1.31 2.68 3 1.5 6.1 3.6 0.3 14.6
Jan-12 12 79 58 0.5 88.5 16.2 1.23 2.46 3.3 1.5 5.7 3.6 0.5 14.4
Feb-12 42 58 52 0.3 87.4 15.9 1.35 2.35 3.2 1.2 6.6 3.5 0.6 15.3

t
Mar-12 4 4 56 0.7 86.8 15.7 1.46 2.78 2.9 2 6.4 3.4 0.5 14
Apr-12 3 3 68 0.6 89.6 14 1.68 3.97 2 2.1 6.3 4.4 0.5 16.8

ip
May12 3 4 72 0.4 97 11.8 1.43 4.35 3.4 1.7 6 3.6 0.4 16.1
Jun-12 15 45 80 0.3 73.7 5.4 1.34 3.93 2.8 1.6 5.8 3.4 0.5 51.5
Average 11 34 64 0.5 91.9 13.6 1.44 3.219 2.9 1.7 6.3 3.8 0.5 18.6
Standard deviation 11 24 11 0.3 4.9 4.9 0.148 0.661 0.4 0.2 0.3 0.4 0.1 10.5

cr
3
4
Table 3 Limiting contents of metals in supernatants (mg/l).

us
5
6
7
Heavy Metals *Long-term use *Term cost Average in supernatant

8
Cd
Cr
Pb
0.01
0.1
5.0
an 0.05
1.0
10.0
0.011
0.064
0.034

9 *The trace elements recommended limits in the treated wastewater for the irrigation in mg/l [27].
M
10
11
12 Table 4 Limiting contents of metals in sludge (mg/kg).
13
d

Heavy Metals *The French standards NF U44 -041 **Alternative Fuels **Alternative Raw **Additions to Cement **Clinker ***Mean in hydroxides sludge
e

Cd 10 5 0.8 1 1.5 0.5

Cr 1000 100 100 200 150 13.6
pt

Cu 1000 100 100 200 100 1440

Pb 800 200 50 75 100 91.9
ce

Zn 3000 400 400 400 500 3219

14
15
16 *Metallic trace elements content limits in mg/kg [28]
17 **Pollution responsible indicators (mg / kg) for the elimination of wastes in cements [29]
18
Ac

***Average in sludge hydroxides in mg/Kg

19
20 Table 4 Correlation matrix between the studied of physico-chemical parameters, heavy metals
21 and trace element.
22

18

Page 19 of 20
 Cd(s) Pb(s) Cr(s) Cd Pb Cr Fe Al Cu Zn P N K C pH(s) pH Tw Ta Cond(s) SM VSS
Cd(s) 1

Pb(s) 0.590 1

Cr(s) 0.027 0.017 1

Cd 0.079 0.069 0.566 1

Pb -0.377 -0.295 -0.572 -0.234 1

Cr 0.373 0.224 0.282 0.815 -0.214 1

Fe -0.720* -0.609 0.020 -0.117 0.039 -0.326 1

Al 0.080 0.240 -0.438 -0.453 0.352 -0.205 -0.466 1

Cu -0.426 -0.716 -0.251 -0.144 0.484 -0.353 0.387 -0.359 1

Zn -0.554* -0.630 0.186 -0.418 0.231 -0.667 0.550 -0.125 0.545 1

t
P 0.207 -0.080 -0.282 0.089 0.365 0.198 0.078 -0.173 0.206 -0.215 1

ip
N -0.433 -0.291 -0.218 -0.089 0.630 -0.282 0.310 -0.387 0.722 0.394 0.281 1

K -0.106 0.045 -0.558 -0.661 0.070 -0.578 0.041 0.156 0.196 0.038 -0.075 0.194 1

C 0.060 0.095 0.380 -0.325 -0.536 -0.592 0.146 -0.106 -0.122 0.412 -0.442 -0.241 0.077 1

cr
pH(s) -0.089 -0.448 0.439 -0.031 -0.510 -0.118 0.529 -0.414 0.148 0.535 -0.240 -0.257 -0.266 0.502 1

pH -0.043 -0.137 -0.115 -0.259 -0.358 -0.151 0.395 -0.375 -0.023 0.034 -0.115 0.001 0.541 0.125 0.247 1

Tw 0.250 0.508 0.373 -0.109 -0.149 -0.357 -0.335 0.204 -0.364 0.119 -0.138 -0.115 -0.077 0.637 -0.138 -0.332 1

us
Ta 0.160 -0.200 -0.044 -0.272 0.332 -0.371 -0.153 0.165 0.281 0.270 0.559 0.168 0.082 0.130 -0.142 -0.302 0.424 1

Cond(s) -0.725 -0.503 0.092 -0.151 0.172 -0.644 0.620 -0.255 0.583 0.706 -0.289 0.435 0.109 0.459 0.312 -0.023 0.146 0.056 1

SM -0.169 0.059 0.087 0.325 0.447 0.032 -0.172 -0.097 0.162 -0.102 0.350 0.520 0.000 -0.256 -0.677 -0.259 0.333 0.433 0.131 1

VSS -0.145 0.061 0.083 0.349 0.444 0.046 -0.194 -0.111 0.187 -0.111 0.340 0.522 -0.002 -0.259 -0.670 -0.267 0.329 0.423 0.142 0.997 1

1
A- Inertia values (%)
an 1
B- Correlation circle of the variables

5,4 pH(s)
M
C
5,2

5,0 Cr(s) pH
Fe
Zn
4,8 Cd(s)
d

Cond(s)
F1 0
Pb(s) Tw
4,6 Cd K
Cr Al Cu
e

4,4
Ta
4,2 P N
pt

4,0 SM Pb
VSS
3,8 -1
ce

-1 0 1
F1=25.20 F2=21.00
F2
C- Factorial map of the campaigns
5
Jun-12
4 Seasonality gradient
Ac

Winter Summer
3
Transient seasons
season: summer

season: winter

Feb-12 Mar-12 Apr-12

1 Jan-12
GIII May-12
F1 0 GII
Dec-11
-1 Nov-11
-2
Oct-11 Sept-11 Jul-11
GI
-3 Aug-11
-4
-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6 7

2 F2

3
4 Fig.1 Graphical approach to the PCA of the physic-chemical parameters and heavy metals
5 according F1XF2.

19

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