Qualitative Status Analysis of the Phreatic Aquifer in the Barlad River Flood Plain concerning the Nitrogen-Based Compounds

Rodica Macale, Doina Dragusin National Institute of Hydrology and Water Management Bucharest, ROMANIA

Abstract:
In order to implement the 2000/60/EC Water Framework Directive in Romania, a qualitative analysis of groundwater in the Barlad River flood plain was made, because it was considered that the groundwater body is at risk from this point of view. The normal concentrations of Ammonium ion were exceeded in 49% of the total number of analyzed mean annual values. The used data comes from 31 observation wells of the Groundwater Quality Monitoring National Subsystem, during 1997 2004. The preliminary data were statistically processsed. The results of this study are represented on GIS maps and charts. The phreatic aquifer is developing in the flood plain and terraces of the Barlad River and its tributaries. From lithological point of view the aquifer is porous-permeable, has large values of hydraulic conductivity and a poor protection of covering deposits, explaining its high vulnerability to pollution. Key Words: Barlad River flood plain, groundwater body at risk, vulnerability to pollution.

Introduction
The implementation of the Water Framework Directive 2000/60/EC in Romania, regarding groundwater, assumed identification, delimitation and characterisation of groundwater bodies on the basis of geological and hydrogeological criteria, of potential and existent anthropic influences upon the groundwater bodies quantitative and qualitative status as well as of some water sustainable management criteria. The groundwater body situated in the Barlad flood plain and terraces, presented in our study, are developed in the eastern side of Romania, in Prut river basin (Fig.1). The area of this body is 1186 km2. Barlad river representes the left tributary of Siret river and it is in charge of Prut Water Directorate.

Figure 1. Location of study area in the Danube river basin

Geomorphological considerations
The Barlad Valley is like a depressionar couloir that enlarged to the south, and has a consistent character both upstream of confluence with Rebricea and downstream of Crasna locality. The absolute altitude of Barlad flood plain varies between 53 m, to the south of Barlad town, and 154 m to the north, in the eastern part of Bacesti locality. Accumulation relief is represented by the terraces, flood plain, alluvial fans etc. The terraces are well developed on the Barlad valley. Beginning to Bacesti locality, on the left of Barlad, there are developed seven terraces, having the following relative altitudes: 3-7 m, 15-20 m, 60-70 m, 100-110 m, 130-135 m, 150-170 m and 190-195 m. The largest development present terraces of 15-20 m and 60-70 m, which appear like smooth plates (Gugiuman et al., 1973). On the tributaries of Barlad river and of the lower streams of Rebricea, Vaslui, Crasna, Lohan, Simila and Tutova valleys are more developed the lower terraces (3-7 m and 15-20 m). The flood plains are the youngest and better representated accumulation forms and they are developed in all valleys independent of their length. Their width is very large in comparison of river or stream bed which formed and pierced them, e.g. 1.5-4 km to Barlad and 1-2 km to Racova , Vaslui, Crasna and Elan. In Barlad flood plain are numerous microforms of relief like: levees, meanders, depressionar forms which retain temporary or permanently meteoric water. They can create swamps and pools of different dimensions, left branches, alluvial fans and small glacis. The main tributaries of Barlad, from Moldavian Plateau are, on the left, Fundatura, Dagata, Sacovat, Stavnic, Rebricea, Vaslui and Crasna and, on the right, Buda and Racova (Fig. 1). The lengths of these streams are comprised between 15 and 65 km. Downstream of confluence with Crasna, Barlad valley is orientated southeastward and receives the tributaries from Tutovei Hill, on the right: Horoiata, Simila, Valea Seaca, Tutova and Pereschivul. The streams Albesti, Idrici, Zorleni, Trestiana, Jeravat, Hobana and Barzota are the left tributaries of Barlad and they move down from Falciului and Covurluiului Hills.

Geological and hydrogeological characterization

Criterium for delineation the groundwater body is the development in the Holocene porous-permeable deposits of the shallow aquifer situated in the flood plain and terraces of the Barlad river and his tributary. The lithological composition of water bearing deposits is the following: sands with gravel elements and argillaceous interbeds. The thickness of permeable deposits is about 2 5 m and it doesnt exceed 10 m (Fig. 2 and 3). Barlad flood plain and terraces contain an unconfined aquifer, who was emphasize through the National Hydrogeological Network wells. The impermeable bed of the phreatic aquifer consists of clays or marls and it was intercepted to the depths between 5 and 20 m. In Ghidigeni area, these deposits can be seen in the cross-section performed on the basis of information given by the hydrogeologic Station wells. (Fig. 4). The thickness of porous-permeable deposits vary between 2 and 10 m. Generally, it can be observed a thickness increasing of these deposits from north to south, from 2-6 m at Ghidigeni zone to 12 m at Tiganesti and 17 m to Tecuci. In Barlad flood plain there were obtained yields of 0.5 2.8 l/sec./well; the aquifer is situated between 7 11 m depth and it is formed from fine and coarse sands and gravels. The lower terrace of Barlad is broken and intensely drained; there are springs with yields of 0.1 0.3 l/sec. to its basis. The yield of the springs that appear at the basis of medium terrace is of 0.5 0.6 l/sec. In the middle basin of Barlad there are a lot of springs that catched by Valea Mare, Valea arinei and Valea Seaca and, the other, from Zorleni, Fagadau and Grivia hills, that are yield of about 1l/sec. The aquifer from terraces was studied in Ghidigeni area by means of many wells. So, the well F32 presents a lithological series that is constituted by an alternation of clays and marls with fine and silty sands. Below a pile of clayey marls there are a fine marly sand with iron oxides situated between 12.05 and 12.95 m. In the deposits of the lower basin of Barlad there is an unconfined aquifer that has, locally, artesian character (the artesian level is 1.5 2 m); these deposits are situated between 2 and 7.5 m depth and are constituted from sand and gravel. Around Barlad town, the flood plain and terraces deposits of Barlad Valley are representated by fine coarse sands and gravels with crossing structure. The overlying stratum consists by thick impermeable deposits of clays, silts and clayey silts (2-10 m thickness).

In many cases, due to impermeable deposits from the cover of aquifer the level is ascensional and sometimes strongly ascensional. At Ghidigeni and Tiganesti, that are situated in flood plains of Barlad river, there are an artesian aquifer at a small depth (until 30 m). Shallow aquifer recharge sources are represented by the river infiltration and precipitation (the effective infiltration is 15 63 mm/year). The groundwater resources from Barlad flood plain are, generally, reduced and the yields obtained from the wells rarely exceed 3 5 l/sec./well. The groundwater resources from Barlad tributary are smaller, respectively (F1 Codaesti) of 1-3 l/sec./well. The hydrogeological parameters values are: the hydraulic conductivity rarely exceed 50 m/day, the values are situated between 1.1 m/day (F1 Condeesti) and 35 m/day (F1 Bacaoani), due to the fine granulometry of deposits; transmissivity has values between 10 100 m2/day (in the Barlad flood plain the transmissivity are higher, of maximum 500 m2/day). The specific yield values are 1 5 l/sec./m, the higher values from this zone were determinated at Torcesti hidrogeological Station (3.65 l/sec./m), at Simila hidrogeological Station (4.20 l/sec./m), at Calieni hidrogeological Station (4.80 l/sec./m) and 8.70 l/sec./m in Serbanesti zone. The fine granulometry of the alluvial deposits, the lens-shaped character of the gravel and the impermeability of the overlying stratum have a negative influence for quantity and quality of phreatic waters, determining a higt vulnerability to pollution. Figure 5 presents the phreatic groundwater body and the position of geological cross-sections trought monitoring wells.

Figure 2. Geological cross-section through the Maraseni hydrogeological Station

Figure 3. Geological cross-section through the Sarbi hydrogeological Station

Figure 4. Geological cross-section through the Ghidigeni hydrogeological Station

Figure 5. Groundwater body delineation into Barlad river basin

Evolution of the Nitrogen-Based Compounds Concentrations

The analyses of the Nitrogen-based compounds concentrations evolution from the Barlad groundwater body was based on the mean annual values provided from 31 monitoring wells for 8 years interval (1997-2004). Groundwater samples from these wells were taken in order to measure the main indicators of the drinking water, according to the Romanian Law No. 458 /2002. From the total number of analysed samples, 11% exceed the maximum admissible concentration for nitrates, 8 % for the nitrites and 49 % for the ammonium.
90 80 70 60 50 40 30 20 10 0 1997 1998 1999 2000 2001 2002 2003 2004

Concentration (mg/l)

Period (year)
DORASTI DORASTI F1 F4 DORASTI DORASTI F2 F5 DORASTI F3

Figure 6. Evolution of nitrates concentration in the wells of the Dorasti Hydrogeological Station

1.00

Concentration (mg/l)

0.80 0.60 0.40 0.20 0.00 1997 1998 1999 2000 2001 2002 2003 2004

Period (year)
DORASTI F2 DORASTI F3 DORASTI F5

Figure 7. Evolution of nitrites concentration in the wells of the Dorasti Hydrogeological Station

2.50

2.00 Concentration (mg/l)

1.50

1.00

0.50

0.00 1997
DORASTI

1998
F1

1999

2000

2001
F2

2002
DORASTI

2003
F3

2004

Period (year)
DORASTI

Figure 8. Evolution of ammonium concentration in the wells of the Dorasti Hydrogeological Station These graphical representations denote the exceedings of the limit value, underlined by the red line (05. mg/l for nitrites and ammonium and 50 mg/l for the nitrates).

The qualitive status and trend assessment of the Nitrogen-based compounds

The Working Group which deals with the European concerning groundwater Directive in CIRCA (Communication Information Resource Centre Administrator), has proposed, in the paper entitled Statistical aspects of the identification of groundwater pollution trends, and agregation of monitoring results (Grath et al., 2001), a methodology in order to asses the qualitative status of the groundwater bodies. In Romania, the National Institute of Hydrology, Departament of Hydrogeology and Environmental Isotopes, has applied this particular assessment methodology (Dragusin, 2004; 2005), following several steps: 1. To calculate the biannual and annual mean value of the nitrates, nitrites and ammonium, for each of the 31 investigated quality monitoring wells, situated on the studied groundwater body; 2. To delimitate the groundwater body, based on the ARCGIS 8.3. software; 3. To delineate the area of the groundwater body (by using the coordinates of the domain in STEREO 70 projection and by saving the files with an *.wmf extension), using SURFER 7 soft;

4. To use the GISView software, which transforms the domain previously delimitated in a GIS matrix which contents 62 rows and 198 columns; 5. To use the GWStat software, after saving the files in the Excel format, following the algorithm presented in the CIRCA Guide (Quo Data Institue, 2001), with the following obtained results: The evaluation of the reprezentativity index (Ru) indicates the value of 21.5%, due to the unidimensional shape of the Barlad groundwater body; The status assessment, for which we obtained the variogram and the following values: the arithmetic mean (AM) = 1.056 with the upper confidence limit (CL(AM)) = 1.567, the Krigging mean (KM) = 1.096 and the upper confidence limit of its (CL(KM)) = 2.233; The monotonic trend assessment denotes a stationary tendency; The reversal trend assessment do not indicates a increasing/decreasing tendency.

Figure 9. Barlad groundwater body polygonal shape in ArcGIS soft

Figure 10. The use of the GISView soft to create the GIS matrix

Figure 11. The previous matrix running in GWStat soft

Figure 12. Trend assessment GIS view in GWStat soft

Figure 13. The variogram and the main statistical parameters obtained for the ammonium mean annual concentration

Figure 14. Monotonic trend assessment in GWStat soft

Figure 15. Trend reversal assessment in GWStat soft

Conclusions
In this paper we analysed the mean annual values of the Nitrogen-based compounds (nitrates, nitrites and ammonium) for a number of 31 wells, belonging to the National Hydrogeological Network, during the1997-2004 period. The most significant exceedings, were registered for ammonium (49% from the total of 282 values). A qualitative risk assessment was made on the Barlad groundwater body, based on the registered exceedings in ammonium. These exceedings have as a potential source the agricultural activities, although in the region an antropic pressure due to industrial activity is known. To underline the exceedings of the above-mentioned indicators of admissible maximum concentration, graphical interpretations were achieved. The charts, presented for the Dorasti Hydrogeological Station, emphasize that the Nitrogen-based compounds contents evolution is hazardously. This paper is also focused on the qualitative status assessment of the Barlad grounwater body, by using the recommendations of the European Community Guide (Grath et al, 2001). The results of the chemical data processing provided from the 31 monitoring wells are: The calculation of representativity index, RU, indicates the value of 21.5%, which is significantly lower than it was recommended by the EU, respectively 80%, but that is the consequence of the unidimensional shape of Barlad groundwater body; The status assessment, for which we obtained the variogram and the following statistical parameters: the arithmetic mean (AM) = 1.056 with the upper confidence limit (CL(AM)) = 1.567, the Krigging mean(KM) = 1.096 and its upper confidence limit (CL(KM)) = 2.233; The monotonic trend assessment, which indicates a general stationary tendency; The reversal trend assessment, which indicates a general hazardous tendency. In order to achieve a complete evaluation of the qualitative status of the groundwater bodies, we consider that some supplementary data, such as the precipitation regime, the soil structure, the temperature values, and the evapotranspiration, should be also included. A connection between the groundwater bodies and the surface bodies waters must be also established.

References
Dragusin, Doina, 2004: Aplicarea Ghidului metodologic de evaluare a starii calitative a corpurilor de ape subterane, propus de Comunitatea Europeana, la acviferele freatice din Romania, I.N.H.G.A. Scientifical Sesion, Apa dulce pentru viitor , Bucharest, Romania Dragusin, Doina, 2005: Evaluarea starii calitative a corpurilor de ape subterane in conformitate cu ghidul metodologic propus de Uniunea Europeana - Aplicare la acviferele freatice din Romania, Romanian Hydrogeological Association Symposium Resursele de ape subterane din Romania Aspecte metodologice n contextul integrarii n Uniunea Europeana, Arcalia, Romania

10

Frugina Elisabeta, Tenu Sanziana, Pirvanescu Elena, 1975: Studiul hidrogeologic de sinteza al bazinului inferior al Siretului. Studii de hidrogeologie, XII, p.5- 57, Bucuresti Gugiuman I., Circota V., Baican V. 1973: Judetele patriei, jud. Vaslui. Ed. Acad. Romane, 133 p., Bucharest Grath, J., Sheidleder, A., Uhlig, S., Weber, K., Kralik, M., Keimel, T., Gruber, D., 2001: Final Report: The EU Water Framework Directive: Statistical aspects of the identification of groundwater pollution trends, and agregation of monitoring results, http://forum.europa.eu.int/ *** Legea privind calitatea apei potabile 458/2002, Monitorul Oficial al Romaniei nr.582/29.07.2002 *** Annex 1 to Final Report User Guide Gwstat, 2001, quo data GmbH Gesellschaft fr Qualittsmanagement und Statistik, Dresden, Germany ***Directive 2000/60/EC du Parlement Europen et du Conseil du 23 octobre 2000 tablissant un cadre pour une politique communautaire dans le domaine de leau, Journal officiel des Communautes europennes, Bruxelles ***Directive 91/676/EEC concerning the protection of waters against pollution caused by nitrates from agricultural sources, Bruxelles (91/676/EEC)of 12 concerning the protection

11