Analele tiinifice ale Universitii Alexandru Ioan Cuza, Seciunea Genetic i Biologie Molecular, TOM XIII, 2012

CORRELATIONS BETWEEN THE GROUPS OF PHYSICAL AND CHEMICAL INDICATORS OF THE SIRET WATER BETWEEN 2008 AND 2009
CRISTINA MAXIM1, CONSTANTIN COCERHAN2, ELENA CIORNEA1*, ELENA TUTU1
Keywords: Pollution, Siret river, water quality indicators, regression line Summary: In the present study aims at making functional links or stochastic ties - correlation based on regression equation right of physical parameters (flow, temperature, pH) and chemical parameters (DO, BOD5, CCOMn, COD) between physical parameters and between chemical parameters. The comparative study was made between the determined values of physical indicators (flow, temperature, pH) and the values of chemical indicators in order to determine correlations between physical and chemical parameters that determine the quality of water and the cumulative effects of pollutants on the values of quality indicators. This study aims at highlighting the existence of a synergistic (cumulative) context of factors, with particular importance in assessing the self-cleaning capacity of surface waters. For this purpose we used experimental data on the mentioned parameters, from the review of water samples from three sites of the Siret river in 2008-2009.

INTRODUCTION
One of the major problems nowadays is the increasingly stronger pollution of the soil, water, air, and therefore of the food. As a EU member country, Romania has committed that by November 2015 it would reach a good ecological status of water bodies. Implementing green technologies must necessarily be accompanied by continuous monitoring of the environment to adopt optimal measures to stop pollution. Because in Suceava County there are many industrial companies, mining companies and potentially polluting livestock farms, we intend to analyze certain chemical and biochemical indicators in the evaluation of the chemical and biochemical oxygen respectively (BOD5, COD-Mn and that COD-Cr) pollution of a tributary water of the Siret river in the county of Suceava. The purpose of this experimental study is to determine physical and chemical indicators, profiling the dynamics of these indicators and the correlation between physical and chemical indicators and between chemical indicators to highlight the link between the dynamics of the Siret River water quality with biotic and abiotic factors closely linked with the biological changes related to the river ecosystem. This study has developed on monitoring the physical and chemical parameters of the water of Siret river from Siret-border locations, Siret-Siret (at 559 km distance from the mouth) and Siret-Huani (487 km from the mouth) during 2008-2009. The following parameters were analyzed: pH, flow, temperature, DO - dissolved oxygen, COD - chemical oxygen demand, BOD5, COD-Mn, COD-Cr. Sampling, preservation and handling of water samples have specific features for each quality indicator and it was done according to "preservation and handling of water samples - FL-18-5 according to STAS 5667 - 3 / 2004" and STAS's applied.

RESULTS AND DISCUSSIONS The correlation coefficient values are presented in Table. 1, compared with 2008/2009 and downstream sites upstream: Siret-border, Siret-Siret, Siret-Huani. Data Table 1 shows a variety of values of the coefficient of correlation both within the same site as well as between sites with few exceptions. DO concentrations at all sites is negatively correlated with temperature, negative linear correlation being strong, the values of the correlation coefficient (R2) ranging between 0.9320 0.7588. This justifies the increase in oxidative processes of organic matter oxidation of nitrogen compounds NH4 and NO3 increases.

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Cristina Maxim et al Correlations between the groups of physical and chemical indicators of the Siret water between 2008 and 2009 Table 1. R2 values of parameters Siret river, period 2008-2009 Site Coef. correl (R2) Flow / DO Flow / CBO5 Temp / CBO5 Temp/ CCOMn Flow /CCOMn Temp / DO DO / CBO5 DO / CCOMn CBO5/ CCOMn Siret border 2008 0.2608 0.4608 0.2698 2009 0.2853 0.4890 0.2320 Siret Siret 2008 + 0.0195 + 0.3251 0.2261 2009 + 0.0100 0.2896 Siret Huani 2008 0.0646 0.1856 0.2822 2009 + 0.0254 0.0384

+ 0.6824 + 0.9687 0.2197 0.7992 0.5482 0.8366

+ 0.0100 + 0.0650 + 0.2130 0.9320 0.0086 0.1083

+ 0.1891 + 0.9277 0.7821

+ 0.1585 + 0.9073 0.7588

+ 0.0044 + 0.9091 0.7645

+ 0.1455 + 0.1351 0.9162

+ 0.1490 0.4928 0.3754

+ 0.1815 0.4585 0.4598

+ 0.2945 + 0.0242 + 0.4763

+ 0.1082 0.3309

+ 0.7718

+ 0.0591

+ 0.0227

For rivers, the largest and typical temporal variability is the flow. This variation causes significant variations in the concentration of ions and other substances transported. The first thought would be that a higher flow leads to lower concentrations by dilution. In practice things are more complex, being able to identify several models. For example, in the flow correlation with chemical indicators we can distinguish: Decreased concentration with increasing flow - Siret border: DO, BOD5, total, Fig. 1, 2 a, b; Changes according to a pseudo gaussian curve, a characteristic of floods - debit/CBO5 Fig.2 b; The curve type loop characteristic variation flood period, when the turbidity reaches a maximum and suspended solids before reaching maximum flow - flow / BOD5 Fig. 2 b; Uneven concentration variation with changes in flow, characteristic of random external inputs of pollutants or phenomena, especially biological, non-flow of water but other factors such as the night/day (night/day), flow / CCOMn, fig 3 c, -it was observed that the irregular variation occurs downstream and it is due to increasing pollution. There is a strong negative linear correlation in all three sites, between temperature and DO concentration, with R2 values in the range 0.7588-0.9320, Fig.4 a, b, c. Regression equations are based on straight lines, knowing the temperature we can estimate the concentration of DO in each location and depending on DO we will estimate balances that may occur and some of the main components of water concentrations. With increasing temperature, increasing microbial activity and therefore nonbiodegradable organic compounds concentrations increased, CCOMn is positively correlated with temperature, reaching R2 value of 0.9687. It appears that chemical parameters are not linearly correlated with each other according to theoretical balance because many chemical and biochemical processes that may occur in water according to various pollutions, accidental over a year. This explains why no significant correlation or functional link has been found between some chemical parameters.

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Flow / DO
16 14 DO (mg O2/L) 12 10 8 6 4 2 0 0 10 20 30 40 50 Flow (mc/s) Siret- border 2008 Siret- border 2009 y = -0.0651x + 11.83 R2 = 0.2608 y = -0.0764x + 12.158 R2 = 0.2853

Flow / DO
16 14 12 10 8 6 4 2 0 0 y = 0.0179x + 10.177 y = 0.0248x + 11.361 R2 = 0.0195 R2 = 0.01

DO (mg O2/L)

Siret-Siret 2008 Siret-Siret 2009

10

20 Flow (mc/s)

30

40

a
Flow / DO
15 DO (mg O2/L) 10 5 0 0 10 20 Flow (mc/s) 30 40 y = -0.04x + 11.224 R2 = 0.0646 y = 0.0281x + 10.097 R2 = 0.0254

Siret- Hutani 2008 Siret - Hutani 2009

c
Figure 1 - Correlation dissolved oxygen (DO)-flow, Siret river, 2008 -2009
Flow / CBO5
2.5 CBO5 (m g O2/L) 2 1.5 1 0.5 0 0 10 20 30 40 50 Flow (mc/s) Siret- border 2008 Siret- border 2009 y = -0.0164x + 1.9047 R2 = 0.4608 y = -0.0171x + 1.89 R2 = 0.4890

Flow / DO
16 14 12 10 8 6 4 2 0 0 y = 0.0179x + 10.177 y = 0.0248x + 11.361 R2 = 0.0195 R2 = 0.01

DO (mg O2/L)

Siret-Siret 2008 Siret-Siret 2009

10

20 Flow (mc/s)

30

40

a
Flow / DO
15 DO (mg O2/L) 10 5 0 0 10 20 Flow (mc/s) 30 40 y = -0.04x + 11.224 R2 = 0.0646 y = 0.0281x + 10.097 R2 = 0.0254

Siret- Hutani 2008 Siret - Hutani 2009

c Figure 2 - Correlation flow CBO5, Siret river, 2008-2009.

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Cristina Maxim et al Correlations between the groups of physical and chemical indicators of the Siret water between 2008 and 2009

Flow / CCOMn
7 6 5 4 3 2 1 0 0 10 20 y = 0.095x + 1.7139 R2 = 0.9277 y = 0.0975x + 1.6727 R2 = 0.9073
CCOMn (mgO2/L) 8 7 6 5 4 3 2 1 0 0 5 10 y = 0.1414x + 2.0056 R2 = 0.9091

Flow / CCOMn
y = -0.0694x + 4.5753 R2 = 0.2197

CCOMn (mg O2/L)

Siret - border 2008 Siret - border 2009

Siret-Siret 2008 Siret- Siret 2009

30

40

50

15

20 Flow (mc/s)

25

30

35

40

Flow (mc/s)

a
Flow / CCOMn
CCOM n (m g O2/L) 8 6 4 2 0 0 10 20 Flow (mc/s) 30 40 Siret - Hutani 2008 Siret - Hutani 2009 y = 0.0606x + 3.726 R2 = 0.1351 y = 0.0515x + 3.989 R2 = 0.2130

c
Figure 3 - Correlation flow CCOMn, Siret river, 2008-2009
Temperature / DO
15 DO (mg O2 /L) 10 5 0 0 5 10 Temperature (oC) 15 20 Siret - border 2008 Siret- border 2009 y = -0.2373x + 13.074 R2 = 0.7821 y = -0.2599x + 13.461 R2 = 0.7588
20 DO (mg O2/L) 15 10 5 0 0 5 10 15 20 25 Temperature (oC) Siret- Siret 2008 Siret- Siret 2009

Temperature / DO
y = -0.1862x + 12.199 R2 = 0.7645 y = -0.2029x + 13.602 R2 = 0.7992

a
Temperature / DO
15 DO (mg O2/L) 10 5 Siret-Hutani 2008 0 0 10 20 30 Temperature (oC) Siret-Hutani 2009 y = -0.2077x + 13.002 R2 = 0.9162 y = -0.2383x + 13.404 R2 = 0.9320

c
Figure 4 - Correlation temperature DO, Siret river, 2008-2009

An uneven concentration variation with changes in flow, characteristic of random external inputs of pollutants or phenomena, especially biological, non-flow of water but other

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factors such as day/night cycle (night / day) - Flow / CCOMn, fig 3 c, - it is noted that the irregular variation occurs downstream and is due to increasing pollution. There is a strong negative correlation, linear in all three sites, between temperature and DO concentration, with R2 values between 0.7588-0.9320, Fig. 4 a, b, c. Based on the regression equations of the straight lines, knowing the temperature we can appreciate the concentration of DO in each location and based on DO we will provide balances that may occur and some of the main components of water concentrations. When temperature increases so does the microbial activity and, therefore, the concentration of non-biodegradable organic compounds concentrations increase, CCOMn is positively correlated with temperature, reaching R2 value of 0.9687. It appears that chemical parameters are not linearly correlated with each other according to theoretical balance because of many chemical and biochemical processes that may occur in water as well as various, accidental pollutions over a year. This explains the fact that no significant correlation between some chemical parameters or functional link has been found. In the process of systematization and data processing we must take into account optimal sampling points analyzed with considerable influence on the quality of test results (Vandenberghe, 2002).
Temperature / CBO5
CBO5 (m g O 2/L) 2.5 2 1.5 1 0.5 0 0

Temperature / CBO5
CB O 5 (m g O 2/L ) 5 4 3 2 1 0 0 y = -0.0395x + 2.1317 y = 0.075x + 2.0255 R2 = 0.6824 R2 = 0.2261 Siret- Siret 2008 Siret- Siret 2009 5 10 15 20 25

y = -0.0264x + 1.8899 R2 = 0.2698

y = -0.0245x + 1.8512 R2 = 0.2320

Siret- border 2008 5 10

Siret- border 2009 15 20

Temperature (oC)

Temperature (oC)

a
Temperature / CBO5
CBO5 (mgO2/L) 4 3 2 1 0 0 y = -0.0316x + 2.5936 R2 = 0.2822 y = 0.0081x + 2.5442 R2 = 0.010

Siret-Hutani 2008 5 10 15

Siret - Hutani 2009 20 25 30

Temperature ( oC )

c
Figure 5- Correlation temperature CBO5, Siret river, 2008-2009

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Cristina Maxim et al Correlations between the groups of physical and chemical indicators of the Siret water between 2008 and 2009

Temperature / CCOMn
CCOMn (mg O2/L) 8 6 4 2 0 0 5 10 Temperature (oC) Siret- border 2008 Siret- border 2009 15 20

Temperature / CCOMn
CCOMn (mg O2/L) 8 6 4 2 0 0 5 10 15 20 25 Temperature (oC) Siret- Siret 2008 Siret - Siret 2009 y = 0.0164x + 3.851 R2 = 0.0044 y = 0.134x + 2.5617 R2 = 0.9687

y = 0.0903x + 2.417 R2 = 0.1891

y = 0.0849x + 2.435 R2 = 0.1585

a
CCOMn (mg O2/L )

b
Temperature / CCOMn
8 6 4 2 0 0 10 20 30 Temperature (oC ) Siret - Hutani 2008 Siret - Hutani 2009 y = 0.0867x + 3.5025 R2 = 0.1455 y = 0.0398x + 4.0358 R2 = 0.0650

c
Figure 6 - Correlation temperature CCOMn, Siret river, 2008-2009

DO / CBO5
CBO 5 (m g O 2/L) 3 2 1 0 0 5 DO (mg O2/L) 10 15
CBO5 (m g O2/L)

DO / CBO5
5 4 3 2 1 0 0 y = 0.2116x - 0.45 R2 = 0.2945 Siret - Siret -2008 Siret- Siret-2009 y = -0.2961x + 6.1997 R2 = 0.5482

y = 0.0732x + 0.8441 R2 = 0.149 Siret- border 2008 Siret- border 2009

y = 0.0727x + 0.8168 R2 = 0.1815

10 DO (mg O2/L)

15

20

a
DO / CBO5
CBO5 (mg O2/L) 4 3 2 1 0 0 5 10 DO (mg O2/L) 15 Siret- Hutani 2008 Siret-Hutani 2009 y = 0.0901x + 1.2832 R2 = 0.1082 y = -0.0306x + 2.9647 R2 = 0.0086

c
Figure 7- Correlation DO CBO5 , Siret river, 2008-2009

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DO / CCOMn
C CO M n (m g O 2/L ) 8 6 4 2 0 0 5 DO (mg O2/L) 10 15
CCO M n (m gO2/L)

DO / CCOMn
y = -0.4841x + 8.549 R2 = 0.4585
8 6 Siret- Siret 2008 4 2 0 0 5 10 DO (mg O2/L) 15 20 Siret- Siret 2009 y = 0.1803x + 2.1263 R2 = 0.0242 y = -0.5485x + 10.244 R2 = 0.8366

y = -0.5432x + 9.1391 R2 = 0.4928 Siret- border 2008 Siret- border 2009

a
DO / CCOMn
8 6 4 2 0 0 CCOMn (m g O2/L) y = -0.6024x + 10.919 R2 = 0.3309 Siret- Hutani 2008 Siret- Hutani 2009 5 DO (mg O2/L) 10 15 y = -0.2082x + 6.7034 R2 = 0.1083

c
Figure 8 - Correlation DO CCOMn, Siret river, 2008-2009

CBO5 / CCOMn
7 6 5 4 3 2 1 0 0 CCOM n (m g O2/L) y = -2.5009x + 7.3815 R2 = 0.3754 y = -2.8395x + 7.8416 R2 = 0.4598
8 7 6 5 4 3 2 1 0 0

CBO5 / CCOMn
y = 2.0523x + 0.4014 R2 = 0.4763 y = 1.3171x + 0.2393 R2 = 0.7718

Siret- border 2008 Siret - border 2009 0.5 1 1.5 2 2.5

CCOMn (m g O2/L)

Siret- Siret 2008 Siret- Siret 2009

CBO5 (mg O2/L)

CBO5 (mg O2/L)

a
CBO5 / CCOMn
8 7 6 5 4 3 2 1 0 0 y = 0.9295x + 2.3488 R2 = 0.0591 y = 0.3826x + 3.7459 R2 = 0.0227

CC OMn (mg O2/L)

Siret- Hutani 2008 Siret- Hutani 2009

2 CBO5 (mg O2/L)

c
Figure 9 - Correlation CBO5 CCO-Mn, river Siret, 2008-2009

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Cristina Maxim et al Correlations between the groups of physical and chemical indicators of the Siret water between 2008 and 2009

CONCLUSIONS The Siret river is subject to variations that determine the entry, transport and sedimentation of organic substances and materials. In assessing the overall quality of the water body ecosystem and the chemical analysis of water samples at the same time, the sediments analysis which are of particular importance in chemical and biochemical parameters of water variations was performed. The pH and buffering capacity is one of the most important properties of surface waters, property which makes it possible to function as a medium / support for the development of different organisms. Due to the fact that in most cases, in all three sites, the Siret river water pH is below 8.3 (range of values from 7.5 to 8.3), total alkalinity content is the same as HCO3 -. The alkalinity (HCO3 - and CO32-) of water bodies refers to the amount and type of dissolved ions (anions) that move at alkaline pH scale. Alkalinity indirectly measures the concentration of anions in the water. It is caused by or attributed to the presence of bicarbonates, carbonates, hydroxides, borates (uncommon) silicates and phosphates. The non significant variation of pH indicates lack of acid rain and at the same time reduces the negative impact on the ecosystem. DO values are generally higher upstream and lower downstream decrease in the dry season and increase in the wet season. In some locations inversions have been noticed due to reduced activity, photoperiod and photosynthetic, aquatic plants and enhancing growth in organic matter content of wastewater discharged into the Siret river. The DO distribution has a strong effect on the solubility of inorganic nutrients and thus change the redox potential of the aquatic environment, so the value of the DO can be determined if the environment is aerobic or anaerobic. O2 solubility in water is controlled by several major factors, namely: temperature, salinity, pressure and water turbulence caused by wind, currents and waves. Rough surface of the water helps to increase the solubility of O2 dissolved in water. The dynamics of the oxygen regime is determined by the same factors as the dynamic of DO. They fall within the maximum permitted levels for water quality I, with some exceptions due to accidental pollution factors. The DO concentration at all sites is negatively correlated with temperature, the negative linear correlation is strong, the values of correlation coefficient (R2) ranging between 0.9320 0.7588. This justifies the increase in oxidative processes of organic matter oxidation of nitrogen compounds NH4 and NO3 increases. There is a strong linear negative correlation, in all three sites, between temperature and the DO concentration, with R2 values between 0.7588 - 0.9320. Based on the regression equations of straight lines, by knowing the temperature we can estimate the concentration of DO in each location and the function of the DO will provide balances that may occur. It is noted that chemical parameters did not correlate linearly with each other according to theoretical balance because of many chemical and biochemical processes that may take place in water as well as various accidental pollutions that may occur over a year. This explains the fact that no significant correlation between some chemical parameters or functional link has been found. All the conclusions presented above show that the assessment of water quality (and hence the possibility of its use for various purposes) is a highly complex activity. The mere existence of precise results of a large variety of organoleptic analysis, physical, chemical, without any parallel in biological and bacteriological analysis results appears insufficient for a correct interpretation, determining causality, prediction of evolutionary trends and other elements necessary to establish

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an appropriate management. It requires interdisciplinary collaboration between biologists, chemists, physicists, geographers/hydrologists, geologists, meteorologists, physicians, IT tools etc. It is therefore necessary that the water quality monitoring activity observations and standardized measurements continue in the long run, in order to know and evaluate the parameters characteristic of water management and to define the status and trend of development of their quality and highlighting the permanent status of water resources. Finally, society must realize that by preserving the quality of the water it supports economic development and welfare and that quality water is vital in all areas of activity - agriculture, industry, transport, tourism - it is indispensible for recreational activities, it is essential for regulating climate, natural ecosystems and it is an element that gives charm and beauty to natural landscapes. REFERENCES
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