3.4. Determination of metal concentrations in vegetation samples

The toxic effect of the metals in the tissues and plant cells varies according to the concentration, leading that at high concentrations the whole process of plant growth and development is inhibited. Plants heavily suffer due to the harmful action of impurities from polluted air, their behavior representing a good indicator of pollution.

The ability of removing metals is a general characteristic of the organisms tolerant to metals. Many organisms/plants instead to eliminate metals accumulate them in high concentrations, especially in roots and leaves. The manner in which plant metabolism responds to the exposure at different concentrations of heavy metals is an important step in determining the fate of plants, tissues, or cells and their ability to survive. Metal tolerance issues related to development are increasingly the focus of researchers [25].

The ability of plants to takeover chemical elements varies within a wide range. Elements such as Br, As, B, Cs, and Rb are easily taken, while others such as Ba, Ti, Zr, Sc, Bi, Ga, and Fe are less available; these aspects are being adjusted depending on the particularities of the soil plant. Specific to the fungi, these show an affinity for taking over metals like Hg, Cd, Se, Cu, and Zn. The problem of heavy metal pollution of soil and plants in the general context of ensuring the health of living beings (humans, animals, plants), avoiding disturbance on the balance of the ecosystem and the need to address and to elucidate issues related to quality greenhouse products in order to improve culture techniques without soil, requires intense monitoring differences in the content of pollutants in the plant.


Table 8. Comparative situation for metal concentration in soils.

We also considered in our work the characterization of vegetation samples from surrounding areas of raw water reservoirs. We noticed that higher concentrations were found in moss than in leaves, so they accumulate more quickly the toxic metals. Also, there was observed a concentration of heavy metals in aquatic plant tissues; in the same area of sampling, analyzing samples of terrestrial and aquatic vegetation, we observed higher concentrations values of Fe, Co, Ni, Zn, As, and Pb in the lacustrine vegetation. So there is the possibility of using certain plant species for "extracting" the potential toxic heavy metals from water. Table 10 contains the metal concentrations of vegetation collected in May 2011, while Table 11 presents the comparative data for soil‐vegetation.

ensuring the health of living beings (humans, animals, plants), avoiding disturbance on the balance of the ecosystem and the need to address and to elucidate issues related to quality greenhouse products in order to improve culture techniques without soil, requires intense

As March 12.36 14.67 10.72 13.06 16.74 39.64 40.05 27.87

Cu March 16.63 21.03 5.15 20.34 28.64 55.6 73.23 80.54

Pb March 48.6 54.4 29.44 49.06 32.26 15.68 10.86 12.42

Zn March 102.25 65.12 26.96 108.71 49.2 66.79 106.89 102.85

Cd March 0.32 0.27 0.06 1.96 0.21 0.43 0.58 0.16

Ni March 17.07 22.74 11.93 25.21 28.65 48.08 52.04 21.32

Cr March 24.26 36.39 12.11 45.31 37.46 56.6 34.16 24.05

Mn March 304.55 265.56 127.98 324.06 679.78 387.65 250.13 205.02

Co March 8.75 11.00 3.57 4.25 12.4 24.55 20.71 17.12

July 16.95 26.27 28.62 93.30 169.74 53.41 90.18 33.73 September 82.67 25.22 21.36 13.18 25.88 67.62 19.51 49.58

July 37.21 15.37 13.4 60.53 39.01 52.86 74.87 121.06 September 58.54 13.7 14.88 45.31 45.9 67.71 10.68 21.09

July 32.56 23.56 21.27 73.06 18.82 20.13 19.84 21.06 September 19.63 17.32 17.73 77.55 19.5 43.70 14.78 24.12

July 53.85 61.03 55.7 432.00 59.87 77.18 146.37 55.27 September 141.59 61.14 58.46 333.33 86.49 112.76 50.44 98.84

July 0.27 0.23 0.20 1.95 0.27 1.70 1.64 0.14 September 0.77 0.18 0.12 1.95 0.27 0.8 0.08 0.30

July 21.09 15.13 15.03 32.81 33.18 40.31 100.92 17.39 September 93.59 34.84 17.1 44.69 76 73.13 13.44 21.76

July 20.95 23.03 27.28 50.73 59.72 47.51 59.76 24.04 September 65.94 26.23 32.06 55.13 68.99 86.54 7.98 36.48

July 220.33 207.68 235.08 376.52 289.36 1434.76 655.86 228.02 September 224.33 321.63 220.06 1077.88 635.78 600.5 371.23 186.09

July 8.96 7.12 7.81 19.13 13.35 33.34 23.07 15.82 September 11.93 7.25 8.96 18.55 16.45 29.68 6.69 9.01

Area sampling/metal concentrations (mg kg−<sup>1</sup>

Area 1 Area 2 Area 3 Area 4 Area 5 Area 6 Area 7 Area 8

)

We also considered in our work the characterization of vegetation samples from surrounding areas of raw water reservoirs. We noticed that higher concentrations were found in moss than

Table 8. Comparative situation for metal concentration in soils.

monitoring differences in the content of pollutants in the plant.

Elements Period sampling

282 Water Quality


VN, normal values; PA, threshold alert; PI, intervention threshold [24].

Table 9. Element concentrations for 3 years of sampling (mg kg-1).


Table 10. Metal concentrations in vegetation collected in May 2011, from the studied areas.


Table 11. Metal concentrations in soil and vegetation samples from July 2011.

### 3.5. Drinking water

The surface water pollution's main impact in the studied area is on the water processing plant in terms of providing potable water. The drinking water released from the water treatment plant at good quality parameters and distributed through the public network could reach the end users at a less quality level, in which the distribution network of water may represent a potential source of chemical contaminants in the processed water. All the investments undertaken for the rehabilitation and modernization of water supply chain have as final aim the improvement in water quality. Even if the public distribution of water from sources and treatment facilities to the networks and connections are upgraded, there is a gap in the rehabilitation of some buildings internal networks, and thus, water with appropriate quality to the branch may get degraded to the end user tap due to the poor state of the interior outdated pipes.

Due to the increasing influence of the anthropogenic factors on water sources, the ensuring of water quality is of primary importance. At global level, the environmental monitoring is assured by the IGBM (integrated global background monitoring of environmental pollution) and GEMS (global system of environmental monitoring) networks. IGBM deals with background monitoring (before the intervention of pollution), and GEMS follows the impact monitoring (after the intervention of pollution). Over 20 EEC Directives regarding the protection of aquatic environment and many guidelines laying down the quality standards regarding the use of water and the checking of wastewater discharge are in force to support these activities (e.g., Council Directive 76‐464‐EEC—pollution caused by the discharge of dangerous substances into the aquatic environment; Council Directive 88/20/EEC—limit values for discharges of certain dangerous substances). Metals with potentially harmful effect on groundwater are Zn, Cu, Ni, Cr, Pb, Se, As, Sb, Mo, Ti, Sn, Ba, Be, Bi, U, V, Co, Tl, Te, and Ag. The maximum permissible limits for metal concentrations in drinking water given by some international directives are shown in Table 12.


Table 12. Permissible limits, in μg L−<sup>1</sup> , for drinking water in England (NS300), European Union (EU), United States of America (USA) and Romania.

3.5. Drinking water

Elements

284 Water Quality

Elements

The surface water pollution's main impact in the studied area is on the water processing plant in terms of providing potable water. The drinking water released from the water treatment plant at good quality parameters and distributed through the public network could reach the end users

Sampling area/metal concentrations (mg kg−<sup>1</sup>

Leaves Moss Leaves Leaves Leaves Leaves Leaves Leaves Moss

Sampling area/metal concentrations (mg kg−<sup>1</sup>

Soil Vegetation Soil Vegetation

Area 1 Area 3

Co 8.96 0.13 7.81 1.13 V 48.67 0.17 58.72 0.22 Ni 21.09 1.72 15.82 2.69 Cu 37.21 2.54 13.40 6.10 Zn 53.85 48.26 55.70 36.32 As 16.95 0.15 28.62 0.34 Pb 32.56 0.12 21.27 0.10

)

Area 1 Area 2 Area 3 Area 4 Area 5 Area 6 Area 7

Ti 44.78 283.50 47.64 121.20 223.20 23.16 41.64 55.34 236.95 V 0.90 31.83 0.47 11.65 21.09 0.34 0.21 2.71 69.19 Cr 3.38 17.44 1.28 9.09 17.28 2.07 1.37 2.62 45.07 Mn 47.74 257.27 41.98 196.11 399.35 93.22 76.17 79.23 252.88 Fe 357.01 9104.51 161.19 3147.62 5580.78 109.56 98.10 631.14 11290.76 Co 0.24 5.62 0.33 2.10 4.47 0.24 0.67 0.86 7.87 Ni 2.05 11.04 2.89 4.72 10.09 3.13 2.15 5.88 24.75 Cu 8.52 20.02 19.34 10.50 19.11 14.51 8.32 20.73 18.75 Zn 44.78 79.84 33.91 32.75 44.88 27.43 27.38 51.31 54.50 As 0.66 11.47 0.36 7.40 13.30 0.66 0.14 2.01 45.97 Cd 0.04 0.72 0.11 0.36 0.35 0.22 0.45 0.95 1.05 Ba 34.23 132.58 64.13 117.8 121.47 26.64 21.40 130.86 703.31 Pb 1.12 35.90 1.88 4.02 8.20 1.84 1.11 1.80 12.25

Table 10. Metal concentrations in vegetation collected in May 2011, from the studied areas.

Table 11. Metal concentrations in soil and vegetation samples from July 2011.

)

In Germany, the maximum permissible limits for drinking water are the same as those for the member states in the EU, exception As (40 μg L−<sup>1</sup> ) and Pb (40 μg L−<sup>1</sup> ). In Spain, the quality criteria for wastewater that may affect quality of surface water has recently been amended, setting values of 50 μg L−<sup>1</sup> for Astotal, 5 μg L−<sup>1</sup> for Cr (VI), and 1 μg L−<sup>1</sup> for Sedissolved. In Romania, certification of potable water is performed in accordance with the Laws 458/2002 and 311/2004, which are aligned with the European Framework water Directive 2000/60/EC (Table 13). They concern the organoleptic (sensory), physical, chemical (general and toxic), radioactive, bacteriological, and biological characteristics of water.


The waters investigated in this study ensure the drinking water sources of the cities from Cluj county, but also provide industrial water for energy purposes and water for a trout farm in the area downstream the dam. The trace elements present in the water supplied as drinking water to population but also in the wastewaters and water of sewage plants before discharging into the rivers were determined for this work. Quality of water at the inlet in the distribution networks versus the one at the household consumer was characterized to highlight potential sources of contamination due to the technical condition of pipe networks. The water quality monitoring consisted of three phases:

i. Monitoring the water quality of Gilau Lake in order to establish a realistic image in terms of physicochemical parameters value of the water before entering the treatment plant samples collected directly from the lake. In terms of toxic metals, the studied surface water fall in first quality class, with few minor exceptions. Overall, the overruns, in the absence of an organized source of pollution, would lead to the conclusion that it is a natural pollution, which could be confirmed geochemical.


In Germany, the maximum permissible limits for drinking water are the same as those for the

criteria for wastewater that may affect quality of surface water has recently been amended, setting values of 50 μg L−<sup>1</sup> for Astotal, 5 μg L−<sup>1</sup> for Cr (VI), and 1 μg L−<sup>1</sup> for Sedissolved. In Romania, certification of potable water is performed in accordance with the Laws 458/2002 and 311/2004, which are aligned with the European Framework water Directive 2000/60/EC (Table 13). They concern the organoleptic (sensory), physical, chemical (general and toxic),

2011 Water treatment plant Raw water 0.302 <0.001 0.002 0.338 0.102

2010 Gilău treatment plant Raw water 0.220 <0.001 0.003 0.244 0.101

2009 Water treatment plant Raw water 0.345 <0.001 0.007 0.453 0.078

City water entry point 0.229 <0.001 0.003 0.230 0.076

City water entry point 0.184 <0.001 0.002 0.201 0.101

City water entry point 0.298 <0.001 0.005 0.392 0.069

The waters investigated in this study ensure the drinking water sources of the cities from Cluj county, but also provide industrial water for energy purposes and water for a trout farm in the area downstream the dam. The trace elements present in the water supplied as drinking water to population but also in the wastewaters and water of sewage plants before discharging into the rivers were determined for this work. Quality of water at the inlet in the distribution networks versus the one at the household consumer was characterized to highlight potential sources of contamination due to the technical condition of pipe networks. The water quality

i. Monitoring the water quality of Gilau Lake in order to establish a realistic image in terms of physicochemical parameters value of the water before entering the treatment plant samples collected directly from the lake. In terms of toxic metals, the studied surface

) and Pb (40 μg L−<sup>1</sup>

Decant water 0.250 <0.001 0.016 0.147 0.010 Filtered water 0.165 0.007 0.033 0.284 0.041 Chlorinated water 0.221 <0.001 0.005 0.255 0.026

Decant water 0.125 <0.001 0.002 0.159 0.058 Filtered water 0.247 0.003 0.078 0.245 0.105 Chlorinated water 0.234 <0.001 0.010 0.228 0.114

Decant water 0.236 <0.001 0.012 0.245 0.056 Filtered water 0.188 0.101 0.051 0.387 0.074 Chlorinated water 0.268 <0.001 0.003 0.368 0.066

). In Spain, the quality

Metal concentrations (μg L-1)

As Cd Pb Co U

member states in the EU, exception As (40 μg L−<sup>1</sup>

Area/sampling period

286 Water Quality

monitoring consisted of three phases:

radioactive, bacteriological, and biological characteristics of water.

Table 13. Characterization of waters from water treatment plant (entrance to city).

The water samples were collected from many urban districts. Comparing the obtained data with the permissible values in Romania, we can state that in terms of toxic metals content the drinking water is adequate and is well below the admissible limits (Table 14).


Table 14. Characterization of metal concentrations in waters from urban distribution areas.
