THE ASSESSMENT OF GROUNDWATER IN DOLJCHIM CHEMICAL...

Geographica Timisiensis, vol. 18, nr. 1-2, 2009 (pp. 181-192) ●

THE ASSESSMENT OF GROUNDWATER IN DOLJCHIM CHEMICAL PLANT AREA

Sanda Adina ŞERBAN

Direcţia Apelor Jiu Craiova Marioara ŞERBAN

Grupul Şcolar Agricol Dăbuleni

Abstract: Groundwater is the biggest fresh water reservoir in the world and it represents more than 97 % of all available fresh water reserve, excluding the glaciers. The groundwater is very important for the hydrologic cycle and is vital for wetlands and river flow, acting as a reservoir in drought periods. The groundwater has specific physicochemical properties and may be used as drinking water for population. In Romania, about 83 % of the water used for population comes from underground, and for this reason it is very important to keep the groundwater unpolluted. The development of different industries and urban expansion (without sewage network and waste water treatment plant), the intense agriculture led to a damaged environment.The water pollution is a process that modifies its specific physicochemical and biological properties, which led to restriction or special measures of decontamination so the water may be used for different activities. The purpose of this paper is to assess the harmful effects on the environment, especially on groundwater of the pollution made by Doljchim Chemical Plant that affects, so far, only the phreatic sheet. In the Doljchim Chemical Plant area the groundwater physicochemical parameters were analysed. The obtained values have shown big concentration at the nitrogen compounds. Although, over the years, the treatment of the waste water from the chemical plant was improved, the pollution of phreatic sheet remains and all because of the diffuse pollution that is very hard to control. Rezumat: Evaluarea apelor subterane în arealul întreprinderii Doljchim. Apele subterane constituie cel mai mare rezervor de apă dulce din lume, reprezentând mai mult de 97% din toate rezervele de ape dulci disponibile pe glob, excluzând gheţarii şi calotele glaciare. Apele subterane joacă un rol important în ciclul hidrologic şi sunt vitale pentru păstrarea zonelor umede şi a curgerii în râuri, acţionând ca un rezervor tampon în perioadele secetoase. Apele subterane prezintă caracteristici fizico-chimice deosebite, ele constituie o rezervă ce poate fi folosită pentru alimentarea cu apă potabilă a populaţiei. În România, aproximativ 83 % din apa folosită în scop potabil este de origine subterană, motiv pentru care calitatea acesteia trebuie păstrată. Dezvoltarea diverselor ramuri industriale, extinderea aglomerărilor umane ( fără a fi conectate la canalizare sau staţii de epurare), chimizarea excesivă a agriculturii, au condus la degradarea mediului, inclusiv a calităţii apelor subterane. Prin poluarea apelor se înţelege fenomenul de modificare a proprietăţilor fizico-chimice şi biologice ale acesteia ce conduce la restricţii sau măsuri speciale de depoluare pentru ca apa să fie folosită în diferite activităţi în care este necesară. Scopul acestei lucrări este de a demonstra efectele nocive produse asupra mediului, in special asupra apelor subternane, de către Combinatul Doljchim Craiova, poluare ce afectează deocamdată doar pânza freatică. În urma analizelor fizico-chimice efectuate apelor subterane din zona Combinatului Doljchim s-au înregistrat valori foarte mari ale concentraţiilor ionilor de amoniu, azotit şi azotat. Deşi de-a lungul anilor s-au îmbunătăţit metodele de epurare a apelor uzate provenite de la combinat, poluarea difuză constituie încă o problemă ce va trebui rezolvată.

● The assessment of groundwater in DOLJCHIM chemical plant area 182

Key words: water framework directive, groundwater body, chemical plant, nitrate ion Cuvinte cheie: directiva cadru pentru apă, corp de apă subteran, combinat chimic, ion azotat

1. INTRODUCTION

Groundwater is the biggest fresh water reservoir in the world and it represents more than 97 % of all possible fresh water reserve, excluding the glaciers. The groundwater is very important for the hydrologic cycle and is vital for wetlands and river flow, acting as a reservoir in drought periods.

Over the years, a lot of theories about the origin of groundwater have been elaborated. Many scientists were the advocates of the water infiltration and devaporation theory. The waters that circulate and stagnate in the lithosphere are known as groundwater.

According to the Directive (80/68/CEE) for the protection of groundwater from chemical pollution, groundwater is represented by all water under the soil surface, in the saturated area and in contact with the soil and subsoil.

The water infiltrates through permeable rocks until the impervious rocks, begins to saturate the empty spaces and to form aquifers. These rocks are characterized by hydrogeological properties such as: porosity, permeability, capacity of absorption.

The water moves inside the ground with different velocity and in various directions (vertical, horizontal or laminar).

The groundwater has specific physicochemical properties and may be used as drinking water for population. In Romania, about 83 % of the water used for population comes from underground and for this reason it is very important to keep the groundwater unpolluted.

The development of different industries and urban expansion (without sewage network and waste water treatment plant), the intense agriculture led to a damaged environment.

The water pollution is a process that modifies its specific physicochemical and biological properties, which led to restriction or special measures of decontamination so the water may be used for different activities.

According to the legislation, the quality of groundwater is protected by European Directives, many of them fully transposed in the Romanian legislation. The most important are: the Water Framework Directive (60/2000 CE), the Directive for the protection of groundwater against pollution and deterioration (2006/118/CE), the Directive for the protection of groundwater against nitrates pollution from agricultural sources (91/676 CE ).

Through the Directive for the protection of groundwater against pollution and deterioration (2006/118/CE) it is imposed to member states to prevent the direct or indirect discharge of waste water with dangerous substances in the groundwater and to reduce the discharge of other pollutants, in order to avoid pollution.

The Water Framework Directive (2000/60/CE) regarding the establishment of the frame for European policy in water field has integrated the provisions from the Groundwater Directive in one complex system meant to assure the quality and quantity of all groundwater in the European Union. The Water Framework Directive established environmental objectives for groundwater, surface waters, coastal and transitional waters that must be achieved by the end of 2015.

Sanda Adina ŞERBAN, Marioara ŞERBAN ● 183

The Article 17 from Water Framework Directive provides information on the general settlements for groundwater from European Union through technical analyses of water body characteristics, pressure and impact analysis, monitoring program and programs of measures. These technical analyses are well described in the new groundwater directive (2006/118 CE) and they contain criteria for the evaluation of chemical status, for the identification of pollution tendency, for the program of measures in order to prevent or to reduce the waste water discharge in groundwater.

The pollution of groundwater is in fact the discharge of waste waters made by human, directly or indirectly, with major consequences for human health and water intake.

The chemical substances from waste waters that can damage the groundwater may be in three aggregation stages: solid, liquid or gas. The solids may enter in contact with groundwater especially in solution, through a solvent (the most frequent solvent is water) or in very small particles. The liquid or gas pollutants may enter in the groundwater just like that or carried away by another liquid.

There are three major factors that contribute to groundwater pollution: a) Natural factors, represented by:

Conductivity coefficient of Darcy’s law which reveals both the properties of the solid phase ( granularity, porosity, shape, solids particle disposition, temperature ) through the intrinsic coefficient of permeability and the properties of the liquid phase ( specific weight, viscosity ): soil stratification through layers arrangement and continuity, heterogeneity or

anisotropy; the disposition and hydro geological characteristics of the groundwater layer. The

most vulnerable is the phreatic sheet because of its position (close to the surface). The thickness of the groundwater layer is also important. If the water layer is bigger, the dilution phenomenon appears which reduces the potential pollution. The supply and the natural drainage of the aquifer layer can influence the

groundwater pollution, by promoting or not the contamination with chemical substances.

b) Anthropogenic factors are represented by human activities and their effect on groundwater. From this category it can be mentioned:

Industrial activities. It is very well known that every industrial activity imposes a certain water consumption, water intake installations, transportation, treatment and waste water treatment and discharge. In these cases, the groundwater pollution may occur from the water transportation pipes, the insufficient permeability of water storage. The phreatic sheet under an industrial platform is always polluted with chemical substances that are used in that industrial branch. The hydro morphological alterations, like dams, water course regulation, erosion

control measures are influencing the groundwater flow from the bordering area. c) The technical and economical factors are very important and impossible to leave out.

In Romania the massive industrialisation began in sixties and only in the last years was shown an interest towards environment protection. The main objective was the productivity. Once Romania join the European Union, has begun the harmonisation of the European and Romanian legislation. Today, all Environmental European Directives are transposed in the Romanian legislation and efforts are made to implement these directives.


The main technical and economical factors that are influencing the pollution of groundwater are: The necessity of examination the new industrial objectives through environment impact studies going on the principle that is better to prevent than to decontaminate the groundwater; The observance of technology discipline for all production and waste water treatment processes; The monitoring of all noxa agents evacuated in air, water and soil in order to know the pollution stage and the possible “ accidental pollutions “ that may occur;

The inobservance of these factors can lead to environment pollution, situation encountered in many industrial Sites in Romania.

The purpose of this paper is to demonstrate the harmful effects on the environment, especially on groundwater by the Chemical Plant Doljchim Craiova, pollution that is affecting so far only the phreatic sheet.

2. METHODS USED

To assess the quality of groundwater in the area of Doljchim Chemical Plant several aspects were taken into account:

o the choice of the perimeter to be examined; o identification and characterization of the groundwater body which includes the

drillings subject to monitoring; o monitoring of physical-chemical indicators, particularly nitrogen compounds for

drillings subject to review and their change for a period of 30 years. The analyzed perimeter is situated in the vast geographical unit Getic Piedmont,

near its southern limit, at the contact with the southern geomorphologic unit, Oltenia Plain, part of the Romanian Plain. The construction of Doljchim Chemical Plant was begun on September the First, 1961. The first section built was Kellog Ammonia.

In 1965, the plant has entered the sphere of production with 200 thousand tons ammonia / year.

Doljchim Chemical Plant is located at about 10 km north-west of Craiova city, on the National Road to Filiaşi, being located on the lower terrace and the Jiu valley, which required the embankment of the left bank of Jiu river and of the right bank of Amaradia river. The construction works of this industrial objective, as well as its operation, have obviously modified the existing relief, creating a new kind of anthropogenic relief represented by extensive deposits of slimes, water accumulation for abstractions, culvert and return channels, which give a new image to the geography of places.

In the next figure (figure no.1 is represented the geographical location of Doljchim Chemical Plant Craiova).


Fig. 1 Geographical location of Doljchim Chemical Plant Craiova

Amplasarea geografică a Combinatului Chimic Doljchim Craiova

All chemical processes which take place in different sections of the plant have a strong impact on the environment. There are both an air pollution (resulting in particular from combustion processes), and a pollution of surface waters (Jiu and Amaradia emissaries) due to an incomplete cleaning of waste water and a pollution of groundwater due to the deposits of phosphor- ammonia slimes which are not properly permeable.

The analyzed perimeter is in the groundwater body of "Flood plain and Jiu terraces- ROJI05" water body that has been defined using the following criteria:

geologic hydrodynamic the status of the water body (qualitative and quantitative)

Delineation of groundwater bodies was done only for areas where there are significant aquifers as importance for water supplies and certain usable flows more than 10 m3/a day. In the rest area, even if there are local accumulation conditions of groundwater, they do not constitute in water bodies, according to Water Framework Directive 60 /2000/EC.

Geological criteria, occurs not only through the age of water-bearing deposits, but also through the petrographic, structural characteristics, or their ability and properties to


storage water. Thus, there were identified and characterized water bodies of porous, fissure and karst type.

The hydrodynamic criterion acts especially in relation to the expansion of water bodies. Thus, groundwater bodies extend only to the limit of the river basin, which corresponds to their division line, while the deep water bodies may extend outside the basin.

The state of the water body, both quantitative and qualitative, has been a central goal in the delimitation characterization and evaluation process of a groundwater body.

The groundwater bodies that develop in the border area and continue in the territory of neighbouring countries are defined as transboundary.

In Jiu river basin eight groundwater bodies were identified and delimitated. The code of the groundwater bodies has the following structure: RO = country code,

JI =area = river basin, 01 = the number of water body in the Jiu river basin. Of the eight groundwater bodies identified, four are of porous type, accumulated in deposits of quaternary, dacian and sarmatian age, three bodies are karst- fissure type, developed in-cretaceous jurassic deposits and one water body belongs to the fissure type located in burdigalian deposits .

Most groundwaterbodies, as for exemple ROJI01 (Campu lui Neag-Petrila / Petrosani Depression), ROJI02 (Closani-Baia de Arama/Mehedinti Plateau), ROJI03 (Tismana-Dobriţa/Vâlcan Mountains), and ROJI04 (Vârciorova-Nadanova-Ponoarele / Mehedinti Plateau) develop in mountain areas and they are of karst-fissure type, being developed in limestone, marnolimestones or sandstones.

Two groundwater bodies (ROJI05 and ROJI06) were delimitated in areas of meadows and terraces of Jiu River and Danube, being developed in porous-permeable alluvial deposits, of quaternary age. Situated close to the land, they display free level.

The groundwater body under analysis (ROJI05) is a porous permeable type, developed in deposits of meadow and terraces of Jiu valley and its tributaries, being of quaternary age.

The aquifer of meadows and terraces consists of gravels and blocks caught in sandy masses, sometimes sandy clays and even clays.

The groundwater body is of porous permeable type, developed in deposits of meadow and terrace of Jiu valley and its tributaries being of quaternary age.

The aquifer of meadows and terraces consists of gravels and blocks caught in sandy masses, sometimes sandy clays and even clays.

In the area of Getic Piedmont water is accumulated both in alluvial deposits along the rivers (sand, gravels and blocks) and also in Pleistocene sands and gravels inferior attributed to Cândeşti layers. In the meadow areas, the groundwater layers are developed at depths of 2 - 5 m.

In figure no.2 are represented the Groundwater bodies in Jiu River Basin and also the geographical location for Doljchim Chemical Plant and two quality drillings that will be analysed (Işalniţa P1 and Işalniţa P2 ).


0 10 20 30 405km

Varciorova- NadanovaPonoarele

Closani -

Baia de A

rama Tismana - D

obrita

Flood plainand terraces

for JiuDunube -Calafat

Flood plain

Campul lui Neag- Petrila

Tg Jiu

Oltenia

P6

P2Doljchim Chemical Plant

LegendDoljchim Chemical Plant

Groundwaterbody from phreatic sheet

NUMECampul lui Neag- Petrila

Closani - Baia de Arama

Dunube - Calafat Flood plain

Flood plain and terraces for Jiu

Tismana - Dobrita

Varciorova - Nadanova Ponoarele

Drillings for quality surveillance

P2

P6

Jiu river

Jiu River Basin limit

Dunube river

Ground waterbody from depression sheet

ROJI08_Tg Jiu

ROJI07_Oltenia

Fig. 2 Groundwater bodies in Jiu River Basin Corpurile de apă subterană din Bazinul Hidrografic Jiu


3. RESULTS

Before the Doljchim Chemical Plant was build, in the analyzed area, drillings for

quality surveillance in the flood plain of Jiu were executed and also on the terraces in order to monitor the groundwater from that area.

These drillings are situated in the north part of the analyzed area and represent a reference point for the chemical status in the groundwater.

Comparing the first sampling data with the threshold values for drinking water, it was established that for the chemical indicators: ammonium, nitrite, nitrate, chlorate ions the groundwater are not polluted. The obtained results are revealed in table no. 1.

Tab. 1 The concentration of ammonium, chlorate, nitrate, nitrite ions

and pH in the Işalniţa drillings F1, F2, F3, F4, F5, F6, F7 Concentraţia ionilor de amoniu, nitriţi, nitraţi, cloruri şi pH

În forajele Işalniţa F1, F2, F3, F4, F5, F6, F7

Drilling Sampling NH4+ Cl- NO3

- NO2- pH

name data mg/l mg/l mg/l mg/l Threshold values ( G.D. 458/2002 ) 0,5 250 50 0,5 6,5-9,5

Işalniţa F1 22.12.1966 rests 234 0

0,0007 7,4

Işalniţa F2 22.12.1966

UDL* 10 0

0,0007 8,1

Işalniţa F3 22.12.1966 rests 24 4 0,037 7,8


UDL* 10 0

0,0018 8


UDL* 40 0

0,0004 7,8

Işalniţa F6 22.12.1966 rests 14 0

0,0018 7,98

Işalniţa F7 22.12.1966 rests 240 1,5

0,0007 6,9

UDL* under detection limit

In 1978, 13 pollution drillings upstream and downstream the Chemical Plant Doljchim were executed in the phreatic sheet, in order to assess the chemical pollution.

The first chemical analyses had shown that the phreatic sheet was not polluted. The obtained values have demonstrated that only the concentration of nitrite ion was above the limit (comparing with the threshold from drinking water law). In table no.2, the first analyses for Işalniţa pollution drillings are represented. As it can be seen, only the nitrite parameter is above the threshold value.


In this paper it is showed the evolution, in time, of the groundwater quality in the area of Doljchim Chemical Plant. The assessment was made for two quality surveillance drillings (Işalniţa P2 and P6).

Işalniţa Pollution P2 is situated upstream Doljchim Chemical Plant Craiova, and Işalniţa Pollution P6 is situated within the Doljchim Chemical Plant.

Tab. 2 The concentration of main chemical indicators in

Işalniţa pollution drillings Concentraţia principalilor indicatori chimici în forajele de

urmărire a poluării

Surveillance Sampling NH4- Cl- SO4

2- NO3- NO2

- pH Drilling data mg/l mg/l mg/l mg/l mg/l Threshold value ( G.D. 458/2002 ) 0,5 250 250 50 0,5 6,5-9,5 Işalniţa Pollution P1 21.11.1974 rests 24,92 192 4,6 2,3 8 Işalniţa Pollution P2 19.09.1974 rests 70,92 216 31 3 8 Işalniţa Pollution P3 17.10.1974 rests 46,1 72 15,5 4,6 7,3 Işalniţa Pollution P4 12.06.1974 - - 74,05 6,63 0 8,1 Işalniţa Pollution P5 23.11.1974 rests 46,1 240 7,7 0 7,5 Işalniţa Pollution P6 29.06.1974 - 45,5 96,67 6,63 0 7,9 Işalniţa Pollution P9 29.10.1974 - 18 48 6,5 rests 8,3 Işalniţa Pollution P10 20.06.1974 - 24,5 43,19 4,46 0 8,1 Işalniţa Pollution P11 05.06.1974 - 56 92,15 0 0 7,7 Işalniţa Pollution P12 08.06.1974 - 45,5 76,1 0 0 8

Işalniţa Pollution P13 11.06.1974 - 105 191,3 26,52 3 7,8

The variation of chemical parameters: ammonium, nitrite and nitrate ions analysed

in Işalniţa Pollution P2 over the years is represented in table no.3 and figure no.3. Situated upstream the chemical plant, the quality status of this drilling is not so poor. The threshold values are above the limit for all three indicators, but the values are not so high. The analysed period was between 1974 and 2005.

Tab. 3 The concentration of main chemical indicators in

Işalniţa pollution drilling P2 Concentraţiile principalilor indicatori chimici în forajul de urmărire a poluării Işalniţa P2

Surveillance Drilling

Sampling year

NH4+

( mg/l ) NO2

- ( mg/l )

NO3+

( mg/l ) Threshold value ( G. D. 458/2002 ) 0,5 0,5 50 Işalniţa Pollution P2 1974 0 3 31 1976 0 9,2 30,5 1978 0,4 0,1 0,4


1980 0,8 0,4 49 1982 1 0,1 48 1984 10,4 0,05 8,25 1986 0,4 0,07 112 1991 0,4 0,05 34 2001 0,79 0,09 36 2003 1,21 0,05 30,2 2004 1,54 0,08 41,4 2005 0,83 0,029 38,3

Fig. 3 The variation of ammonium, nitrite and nitrate concentration in Işalniţa P2, 1974-2005

Variaţia concentraţiilor ionilor amoniu, nitrit şi nitrat în forajul de urmărire a poluării Işalniţa P2, 1974-2005

The variation of chemical parameters: ammonium, nitrite and nitrate ions analysed in Işalniţa Pollution P6 over the years is represented in table no.4 and figure no.4. Situated within the Doljchim Chemical Plant, the quality status of this drilling is very bad. The obtained values are over the limit for all three indicators. The analysed period was between 1974 and 2005.


Tab. 4 The concentration of main chemical indicators in Işalniţa pollution drilling P6

Concentraţiile principalilor indicatori chimici în forajul de urmărire a poluării Işalniţa P6

Surveillance Drilling

Sampling Year

Ammonium concentration ( mg/l )

Nitrite concentration ( mg/l )

Nitrate concentration ( mg/l )

Threshold value ( G.D. 458/2002 ) 0,5 0,5 50 Işalniţa Pollution P6 1974 0 0 6,6 1976 0,37 0,05 24 1978 0 0,6 0,4 1980 30,8 0,1 6,9 1982 30 0,17 61 1984 162 0,88 190 1986 140 1,5 280 1991 170 6,4 226 2001 99 2,6 1436 2002 98,44 2,8 1726 2003 2147 3,9 1616 2004 2564 2,21 2784 2005 2311 1,31 2294

0

500

1000

1500

2000

2500

3000

1974 1976 1978 1980 1982 1984 1986 1991 2001 2002 2003 2004 2005

Y ear

Ammonium concentration

Nitrite concentration

Nitrate concentration

Ammonium and nitrite threshold value ( 0,5mg/l )Nitrate threshold value ( 50 mg/l )


Fig. 4 The variation of ammonium, nitrite and nitrate concentration in Işalniţa P6, 1974-2005

Variaţia concentraţiilor ionilor amoniu, nitrit şi nitrat în forajul de urmărire a poluării Işalniţa P6, 1974-2005 4. CONCLUSIONS

Groundwater is more important than the surface waters. In case of groundwater

pollution, the decontamination measures are very hard to take. Recent studies demonstrate that industrial pollution is a major reason of concern

because of the leaking from old industrial platforms, deteriorated pipes that transport waste waters to the treatment plant.

At European level, about a third part of groundwater bodies is polluted with nitrates. The groundwater contamination is a global concern for ecologists and public health

authorities because of its great impact on the environment. This is an almost irreversible process with consequences on the water reserve for human consumption.

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Tipored, Bucureşti ( 302 pag ) Savin C-tin., ( 2000 ), Apele subterane din zona Craiova, Editura Tipored, Bucuresti ( 310 pag ) Trîmbiţaşu E., ( 2008 ), Fizico-chimia mediului – factorii de mediu şi poluanţii lor, Editura

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