ECOLOGICAL CHEMIST RY AND ENGINEERING A

Vol. 18, No. 4 2011

Alojzy WOJTAS1, Ma³gorzata D¥BEK 2, Gra¿yna PIOTROWSKA3 and Tadeusz MALINOWSKI4

NITROGEN IN WATER FROM WELLS

ZWI¥ZKI AZOTOWE W WODACH STUDZIENNYCH

Abstract: The research, which encompassed the period from 1981 to 2009, was conducted on water samples collected from 15 wells, 24–103 m in depth, located within the administrative districts of and Ostroda. The results of water analyses were varied depending on the location of a well and year of the study. The waters were characterized by a high content of manganese and iron. Ammonia was found in all the samples except from the wells in Cimochy, Niemsty, in 2005 and in Gucin in 2009. Nitrate(III) and nitrate(V) were determined much less frequently than ammonia. None of the three above-mentioned compounds was detected in three wells in the district of Olecko. Keywords: groundwater, nitrogen, ammonia, nitrates, water quality

In the region of Warmia and Mazury, potable and other water is drawn from the quaternary water-bearing floor [1]. Water quality control indicates that most of this water belongs to Class II. Groundwater from the Quaternary is characterized by an elevated content of iron and manganese [2]. Sometimes, large amounts of ammonia, in excess of 1.5 mg N × dm –3 , as well as nitrates are found in such water samples [2, 3]. Particularly vulnerable to nitrogen pollution are shallow water-bearing layers near pastures, animal breeding farms, settlements without sewerage or sewage treatment plants. The anthropogenic origin of ammonium nitrogen disqualifies most of such waters from being supplied to water pipeworks [4]. Deep groundwater contains ammonia of the geological origin [3]. Its increased content is found in waters which flow through layers of brown coal, peat and lignite [5]. Among the characteristics of such water are alkaline reaction and intensive color.

1 Department of Environmental Chemistry, University of Warmia and Mazury in , pl. £ódzki 4, 10–718 Olsztyn, , phone: +48 60 397 37 72, fax: +48 89 523 39 76, email: [email protected] 2 District Health and Epidemiology Centre, Olecko, ul. Wojska Polskiego 13, 19–400 Olecko, Poland. 3 Department of Chemistry, University of Warmia and Mazury in Olsztyn, pl. £ódzki 4, 10–718 Olsztyn, Poland. 4 Department of Municipal Economy, ul. Zagrodowa 1, 14–105 £ukta, Poland. 638 Alojzy Wojtas et al

Contamination of groundwater may also be the result of its excessive exploitation [4]. Poland belongs to countries with poor water resources. The average annual outflow is about 1600 m3 per capita, while in some other European countries it reaches 4600 m 3 per capita [6]. Therefore, clean water is the greatest wealth of Warmia and Mazury. The purpose of this study has been to examine tendencies in fluctuations of nitrogen compounds found in waters from wells in the districts of Ostroda and Olecko.

Materials and methods

Some of the physicochemical properties of groundwater sampled from wells in the districts of Olecko and Ostroda were analyzed (Fig. 1).

DI STRICT OF OS TR ODA DI STRICT OF OLECK O

Fig. 1. Location of water intakes

In accordance with the binding requirements for water sampling, samples of raw water for laboratory analysis were taken from the following intakes:

Period Commune Location, depth of a well [m] of research Kowale Oleckie Kowale Oleckie (50), Stozne (77), Szeszki (41) 1999–2006 Wieliczki Cimochy (103), Krupin (62), Niedzwiedzkie (56) 1999–2006 Swietajno Swietajno (82), Niemsty (83) 2000–2006 Olecko Gaski (45), Male (67), (52), Szczecinki (76), Olecko (63) 1981–2006 Lukta Lukta (24), Gucin (40) 2007–2009 Nitrogen in Water from Wells 639

Analyses of water samples were carried out in the Laboratory of Municipal Hygiene at the District Sanitary and Epidemiological Station in Olecko and at the Sanitary and Epidemiological Station in Olsztyn. Determination of the physicochemical properties of water relied on the following methods: pH – by potentiometry, electrolytic conductivity – by the conductivity method, ammonia – by Nessler’s method, nitrate (III) nitrates (V), manganese, iron – colorimetrically. The results were processed using the statistical software packages Statistica and Excel. Means, standard deviation, regression equations and correlation coefficients were computed.

Results and discussion

Based on the results of our study, which comprised many wells, it was demonstrated that the quality of drawn water varied, depending on the location of a well and year of the sampling. The analyzed water samples were characterized by a high content of manganese and iron (Tables 1, 2). The values of electrolytic conductivity in 13 wells were on average below 700 mS × cm –1 , except the wells in Niemsty (710 mS × cm –1 ) and Cimochy (708 mS × cm –1 ).

Table 1

Indicators of water quality from wells located in the communes of Olecko and Swietajno –3 –3 –3 –3 –3 dm dm dm dm × × × dm × –1 3 2 4 × cm × S pH Manganese mg Mn Nitrates(V) mg NO Nitrates(III) mg NO Reaction Ammonia mg NH Location of wells Factors Conductivity m Iron mg Fe Min. 452 7.3 0.02 0.00 0.10 0.02 0.51 Max 812 7.6 0.39 0.04 11.10 0.11 4.26 Gaski X 652 7.5 0.15 0.02 5.52 0.06 1.64 SD 150 0.1 0.14 0.02 5.05 0.04 1.53 Min. 505 7.4 0.37 0.00 0.00 0.08 1.93 Gordejki Max 535 7.5 0.69 0.00 0.00 0.13 2.77 Male X 520 7.5 0.53 0.00 0.00 0.10 2.32 SD 15 0.1 0.16 0.02 0.17 Min. 535 7.2 0.41 0.00 0.00 0.06 2.72 Max 577 7.5 0.79 0.00 0.00 0.12 2.81 Lenarty X 556 7.4 0.60 0.00 0.00 0.09 2.77 SD 21 0.2 0.19 0.03 0.05 Min. 560 7.1 0.00 0.00 0.00 0.05 0.70 Max 642 7.8 0.71 0.02 0.89 0.45 5.18 Szczecinki X 593 7.4 0.38 0.01 0.44 0.17 3.72 SD 35 0.3 0.25 0.01 0.37 0.15 1.57 640 i.–mnmm a maximum, – Max minimum, – Min. Gaski Niemsty Swietajno Stozne Oleckie Kowale Olecko

Location Location of wells of wells niaoso ae ult rmwlslctdi h omnso oaeOleckie, Kowale of communes the in located wells from quality water of Indicators i.38740500 .000 2.23 0.01 0.00 0.00 0.5 7.4 398 Min. 0.03 0.00 0.00 0.00 0.04 7.0 469 Min. i.427300 .001 .20.51 0.02 3.24 0.10 0.16 0.00 0.97 0.00 0.02 0.06 0.00 7.3 0.00 0.00 452 0.00 7.2 Min. 0.15 683 7.3 Min. 502 Min. i.427301 .000 .61.05 0.06 0.00 0.00 0.15 7.3 432 Min. a 1 . .900 11 .14.26 0.11 4.94 11.10 0.19 0.04 3.23 0.00 0.39 0.10 0.00 7.6 1.77 0.13 812 0.03 7.3 Max 0.93 737 7.5 Max 547 Max a 8 . .800 .901 1.69 0.16 0.89 0.04 0.28 7.7 489 Max a 9 . .600 .902 3.31 0.23 0.89 0.02 1.46 7.6 591 Max 1.00 0.14 1.55 0.01 0.39 8.1 519 Max D100101 .250 .41.53 0.85 0.04 0.02 5.05 0.02 0.83 0.14 0.02 0.1 0.29 0.77 0.07 150 0.05 0.01 0.1 SD 0.51 0.32 27 0.00 0.1 SD 0.11 23 0.4 SD 23 SD D2 . .500 .900 0.26 0.04 0.41 0.39 0.09 0.02 0.39 0.05 0.01 0.2 0.36 24 0.1 SD 79 SD X X X X X X Factors Factors 5 . .500 .200 1.64 0.06 4.09 5.52 0.18 0.02 2.12 0.00 0.15 0.08 0.00 7.5 0.54 0.44 0.07 652 0.08 0.01 7.3 0.41 0.39 710 0.00 7.5 0.23 525 7.7 486 6 . .300 .201 1.33 0.11 2.84 0.22 0.15 0.02 0.22 0.23 0.01 7.5 0.87 464 7.5 500 Conductivity Conductivity mS × cm –1 mS × cm –1 X

Reaction deviation. standard – SD average, – Reaction ilck n Lukta and Wieliczki

pH pH al et Wojtas Alojzy

Ammonia Ammonia –3 –3 mg NH 4 × dm mg NH 4 × dm

Nitrates(III) Nitrates(III) –3 –3 mg NO 2 × dm mg NO 2 × dm

Nitrates(V) Nitrates(V) –3 –3 mg NO 3 × dm mg NO 3 × dm

Manganese Manganese –3 –3

mg Mn × dm mg Mn × dm contd. 1 Table

Iron 2 Table Iron mg Fe × dm –3 mg Fe × dm –3 srd ititfutae ihnterneo . (Cimoch 6.7 of C to assigned range value standard the exceed the not did within pH determined fluctuated district Ostroda i.–mnmm a maximum, – Max minimum, – Min. odciiyad0104frp,wihcnim h o aiblt fthese of variability low the confirms which pH, research. the for during 0.1–0.4 characteristics and conductivity Oleckie Kowale Gucin Lukta wiedzkie Niedz- Krupin Cimochy Szeszki h ae ecindtrie ntewtrsmlstkni t in taken samples water the in determined reaction water The h tnaddvainfrteeidctr a elgbe e1–5 o electrolytic for 10–150 ie negligible, was indicators these for deviation standard The Location of wells i.547401 .000 .50.95 0.05 0.00 0.00 0.16 7.4 524 Min. i.38740500 .000 2.23 0.01 0.00 0.00 0.00 0.00 0.5 0.02 1.00 0.03 0.00 7.4 1.57 0.77 0.00 398 0.04 0.00 7.0 Min. 1.16 0.00 0.03 526 0.10 0.00 6.9 Min. 3.10 0.00 0.34 479 0.07 0.00 6.9 Min. 0.00 0.16 509 0.00 7.2 Min. 0.00 520 6.7 Min. 698 Min. a 9 . .600 .902 3.31 0.23 0.89 0.05 0.02 0.05 0.38 1.46 14.60 0.17 0.05 7.6 7.61 0.17 4.15 591 0.01 7.7 0.19 Max 2.21 0.08 44.00 671 2.02 0.05 7.7 Max 4.20 0.66 0.94 634 0.23 0.04 7.7 Max 0.00 0.54 573 0.03 7.5 Max 0.59 606 7.5 Max 718 Max a 4 . .600 .901 2.31 0.11 0.89 0.01 0.46 7.8 547 Max D7 . .600 .900 0.41 0.09 0.02 0.39 0.02 0.01 0.11 4.14 0.36 0.04 0.02 0.1 2.42 0.06 0.76 79 0.00 0.2 0.05 SD 0.49 0.02 16.28 44 0.89 0.02 0.3 0.44SD 0.27 0.21 44 0.06 0.02 0.3 SD 0.47 0.17 25 0.02 0.01 0.1 SD 0.36 0.21 36 0.00 0.4 SD 0.11 10 0.2 SD 12 SD X X X X X X X Factors

0 . .700 .201 2.84 0.15 0.01 0.22 0.02 0.01 0.23 9.14 0.87 0.10 0.01 7.5 2.63 4.19 0.04 500 0.12 0.00 7.4 1.85 7.60 0.05 629 0.76 0.02 7.5 3.57 0.37 0.49 523 0.16 0.02 7.5 1.56 0.00 0.30 534 0.08 0.01 7.4 0.28 0.34 557 0.00 7.1 0.25 708 7.5 534 Conductivity mS × cm –1 X irgni ae rmWls641 Wells from Water in Nitrogen

vrg,S tnaddeviation. standard – SD average, – Reaction pH

Ammonia –3 mg NH 4 × dm

Nitrates(III) –3 mg NO 2 × dm asIgonwtrprt [7]. purity groundwater I lass )t . Oek) The (Olecko). 8.1 to y) edsrcso lcoand Olecko of districts he Nitrates(V) –3 mg NO 3 × dm

Manganese –3

mg Mn × dm contd. 2 Table

Iron mg Fe × dm –3 642 Alojzy Wojtas et al

Iron and manganese are among the elements which most often exceeded the set standards. It was found that these elements appeared in amounts above the threshold limits for the class I purity water in fourteen of the examined wells, except the one in Gucin, where, owing to the small amount of manganese (average 0.02 mg Mn × dm –3 ) and iron (average 0.01 mg Fe × dm –3 ), the water was determined to fulfill the criteria for I class purity [7]. Among the analyzed nitrogen compounds, ammonia nitrogen occurred in all water samples although its concentration was variable. The standard deviation calculated from the individual wells ranged from 0.02 to 0.36 in Lukta to 0.36 in Kowale Oleckie. In water samples from the intakes in Szeszki, Stozne, Niemsty, Gaski, Olecko, Lukta and –3 Gucin the ammonia content was below 0.5 mg NH 4 × dm , which corresponds to the first class of water purity. The other tested water intakes, on at least one occasion, contained more ammonia, such as water of class II or even class III water purity [7]. Based on the regression equations, it was noticed that the ammonia content during our study showed an increasing tendency (Table 3). The lowest annual growth rate of this component was found in the water from the wells in Wieliczki (0.0036 mg –3 –3 NH 4 × dm ) and Swietajno (0.0038 mg NH 4 × dm ); the highest appeared in the water –3 from the well in Kowale Oleckie (0.0495 mg NH 4 × dm ). The correlation coefficients for the results from three communes were negligible, but in the communes of Kowale Oleckie (r = 0.36) and Olecko (r = 0.38), some weak correlation was determined.

Table 3 Ammonia content of the regression equation (Y) in groundwater depending on years of research (x) and correlation coefficients (r)

Coefficients Communities Regression equations of correlation (r) 1 Kowale Oleckie Y = 0.0495 × x – 98.6395 0.36 2 Olecko Y = 0.0121 × x – 23.88675 0.38 3 Swietajno Y = 0.0038 × x – 7.2926 n.s. 4 Wieliczki Y = 0.0036 × x – 6.7397 n.s. 5 Lukta Y = 0.0100 × x – 20.0233 n.s. n.s. – non-significant. Nitrates(III) and (V) appeared much less frequently than ammonia in the analyzed water samples. In the district of Olecko, nitrates(III) or (V) were not found in just three wells: Niemsty, Lenarty and Gordejki Male. The concentration of nitrates(V) in the well –3 in Niedzwiedzkie reached 44.0 mg NO 3 × dm in 2005, which corresponds to class III purity [7]. In the district of Ostroda, the concentration of nitrates(V) in Gucin was only –3 –3 slightly higher than the standard, by 1.2 mg NO 3 × dm in 2007 and 4.6 mg NO 3 × dm in 2009.

Conclusions 1. In none of the examined water wells in the district of Ostroda, the concentration of nitrates (III) exceeded the set standards, while the average concentration of nitrate(V) in Nitrogen in Water from Wells 643

–3 the well in Gucin was slightly increased: by 1.2 mg NO 3 × dm in 2007 and 4.6 mg –3 NO 3 × dm in 2009. In the district of Olecko, the wells Niemsty, Lenarty and Gordejki Male contained water free from nitrates(III) and (V). 2. The content of ammonia in groundwater in the commune of Lukta and the wells in –3 Olecko, Niemsty, Szeszki, Gaski, Stozne was below 0.5 mg NH 4 × dm in all years of the study, ie it remained within the threshold values set for the first class of water purity, while in the other water samples, it exceeded the upper threshold by 0.04 to 0.96 –3 mg NH 4 × dm . 3. All the tested water wells located in the districts of Olecko and Ostroda contained more than standard quantities of iron (an average of 0.04–3.89 Fe mg × dm –3 ) and manganese (an average of 0.01–0.71 mg Mn × dm –3 ), except the well in Gucin, located in the commune of Lukta. 4. The results of our determinations of pH and electrolytic conductivity showed little variability in the years of our study, i.e. the pH ranged from 6.7 to 8.1 and the electrolytic conductivity fluctuated from 398 to 812 mS × cm –1 . The average pH values did not exceed the class I standards established for groundwater, but slightly exceeded the limits set up for permissible electrolytic conductivity values in the wells in Niemsty (by 10 mS × cm –1 ) and Cimochy (by 8 mS × cm –1 ).

References

[1] Ró¿añski S. (ed.): Raport o stanie œrodowiska województwa warmiñsko-mazurskiego w latach 1999–2000. Biblioteka Monitoringu Œrodowiska, Olsztyn 2001, Czêœæ I – rok 1999, 88–92. [2] Krajewski Z.W. (ed.): Raport o stanie œrodowiska województwa warmiñsko-mazurskiego w 2003 roku . Biblioteka Monitoringu Œrodowiska, Olsztyn 2004, 90–94. [3] Œwiderska-Bró¿ M.: Ochr. Œrodow. 1992, 1(45), 15–20. [4] Kowal A.L.: Gaz, Woda Techn. Sanit. 2006, 9, 16–20. [5] £omotowski J. and Haliniak J.: Ochr. Œrodow. 1997, 3(66), 15–17. [6] Ma³y Rocznik Statystyczny Polski. Zak³ad Wydawnictw Statystycznych, Warszawa 2008. [7] Rozporz¹dzenie Ministra Œrodowiska z dnia 23 lipca 2008 r. w sprawie kryteriów sposobu oceny stanu wód podziemnych. DzU nr 143, poz. 896.

ZWI¥ZKI AZOTOWE W WODACH STUDZIENNYCH

1 Katedra Chemii Œrodowiska, Uniwersytet Warmiñsko-Mazurski w Olsztynie 2 Powiatowa Stacja Sanitarno-Epidemiologiczna w Olecku 3 Katedra Chemii, Uniwersytet Warmiñsko-Mazurski w Olsztynie 4 Zak³ad Gospodarki Komunalnej w £ukcie

Abstrakt: Przeprowadzone badania w latach 1981–2009 obejmowa³y wody pobrane z 15 studni po³o¿onych na terenie powiatu oleckiego i ostródzkiego, których g³êbokoœæ wynosi³a 24–103 m. Uzyskane wyniki analiz laboratoryjnych wody by³y zró¿nicowane ze wzglêdu na miejsce po³o¿enia studni, jak i rok badañ. Wody te charakteryzowa³y siê zwiêkszon¹ zawartoœci¹ manganu i ¿elaza. We wszystkich próbkach, z wyj¹tkiem studni w Cimochach, Niemstach, Szczecinkach w 2005 r. i w Gucinie w 2009 r., stwierdzono obecnoœæ amoniaku. Azotany(III) i (V) wystêpowa³y w analizowanych wodach znacznie rzadziej ni¿ amoniak. W trzech studniach powiatu oleckiego nie odnotowano obecnoœci ¿adnego z tych sk³adników. S³owa kluczowe: wody podziemne, zwi¹zki azotu, amoniak, azotany, jakoœæ wody