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Abstract: Acid precipitations and analysis of the phenomenon within the context of
environment international conventions. The purviews of international acts: Geneva Convention
(13.11.79) and Espoo Convention (25.02.91) emphasize the necessity of taking measures regarding the
diminishing of polluting substances emanation and evaluation of transboundary impact of the projects
directed to the economic development of the countries. In Republic Moldova the climatic resources are
determined by extern baric centers. The regime of atmospheric circulation is predominant anti cyclonic
with relatively weak activity of atmospheric processes, with a diversity expressed in seasonal circulation
changes. The majority of cyclones pass over RM territory from West, South-West with the average speed
of 20-30 km/hour, maximum 80-90 km/hour. The winds from West, North and North-West are prevailing
with a lower frequency from South and South-West. The average annual speed is of 2,5-4,5 m/sec. The
climatic factors lead to the displacement on RM territory of air masses polluted by substances emanated
from industrial processes from adjacent countries. Along with charcoal consumption increasing since
1973 and increasing of quantities of acid substances eliminated in the atmosphere, the transboundary
impact of polluting substances upon the air basin of RM increased also, which determined the apparition
of acid precipitation. The monitoring of chemical composition of precipitations in the period 1993-2009
showed the presence of acid precipitations in the Republic of Moldova. The value of pH in precipitation
water samples was varying within the limits 2.65 - 10.35. In the period 1990-1998 the quantity of acid
samples out of the total precipitations increased continuously, in the period 1999-2002 a change was
registered, the water samples from precipitations were in the most part neutral and after 2002 until 2009
an increasing of acid sample number is recorded. Among acid gases responsible for precipitation water
acidulation the most important are the sulphur and nitrogen oxides. The sulphur and nitrogen oxides are
eliminated in high quantities in the atmosphere along with the combustion gases and those from
industrial processes. The emanations of sulphur oxides in air space of the Republic of Moldova
constituted in 1990 (year of reference for international conventions) about 230 kt of sulphur oxides, then
decreased to about 10 kt in 2008. The global emanation of sulphur oxides in the atmosphere is evaluated
to approximately 113 mln tonnes/year, of which 98 mln tonnes reach the atmosphere as SO2, 3 mln t as SO3, 9 mln t - sulphates aerosols and 3 mln - H2S. The studies showed that the precipitations
originated from Stratus and Stratocumulus clouds, which absorb the acid pollutants from the lower layers
of the atmosphere, thus from the local pollution sources, are less acid than the precipitation samples
fallen from Cumulonimbus clouds, which are in contact with the superior part of the atmosphere and
which incorporate the pollutants transported by frontal air masses. The content of analyzed ions and the
value of pH in precipitations also depend on the direction and structure of the wind at the high altitude.
When the wind is descendent the concentration of analyzed ions is higher and the samples are more
acid, which prove the contribution of transboundary transfer of acid substances in acid precipitation
forming. The above mentioned facts show than within the international environment Convention the
Republic of Moldova must benefit the compensation of damage provoked to the environment, economy
and population health through transboundary transfer of acid substances.
Key Words: acid precipitations, atmosphere, transboundary transfer, ecological impact, environment
international conventions.
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Ploile acide s-au impus ca problem major odat cu introducerea n anul 1973 a
embargoului la petrolul arab i rile industriale au trecut la utilizarea masiv a
crbuneliu ca agent energetic [13, 15].
Cea mai acid precipitaie atestat documentar s-a produs n localitatea Willing
(SUA) n anul 1978 cu valoarea pH = 2,0. Valoarea medie anual a pH pentru
precipitaiile din Europa este de 4,5, pentru nordul Europei - 4,0. Valoarea medie anual
teoretic a valorii pH a precipitaiilor pentru Republica Moldova calculat de CE a ONU
este de 5,0 [7].
Dintre gazele acide responsabile pentru acidularea ploilor cele mai importante sunt
oxizii de sulf i azot. Ploile acide practic sunt soluii diluate de acizi, n special a acizilor
sulfuric i azotic. Sursele de poluare influeneaz raportul dintre H2SO4 i HNO3 i l
schimb n limitele de la 1:1 pn la 4:1 [5, 8].
Oxidul de sulf n cantiti mari este degajat n atmosfer cu gazele de ardere. n
Europa degajrile de oxizi de sulf constituie circa 30 mln tone pe an, n nord-estul
Canadei - 40 mln tone/an, n Japonia i sud-estul Chinei - 10 mln tone/an. n Republica
Moldova s-au degajat n anul 1990 (an de referin) 230 kt de oxizi de sulf, care a sczut
pn la circa 10 kt n anul 2005. Emisia global a oxidului de sulf(IV) n atmosfer se
evalueaz la circa 113 mln tone/an, din care 98 mln tone ajung n atmosfer sub form
de SO2, 3 mln t - sub form de SO3, 9 mln t - aerosoli de sulfai i 3 mln - H2S [3, 5, 13].
Oxidul de sulf sub aciunea radiaiei solare, oxidanilor i radicalilor liberi se
transform n compui noi sulfai i sulfii, producnd substane acide:
O2 + H2O H2SO3 2H+ + SO3= i
SO2 + O2 SO3 + H2O H2SO4 2H+ + SO4=
Concentraia NOx n atmosfer variaz de la miimi la zecimi de mg/m3. Surse
naturale de producere a oxizilor de azot sunt descrcrile electrice n atmosfer,
incendiile mari, eliminarea din sol. Intensitatea de degajare de la sursele naturale este de
0,27 kg/km2 n 24 ore. Cantitatea mondial a emisiilor antropogene de NOx se estimeaz
la 40-90 mln t/an. La sursele ambigue se refer transformarea NH3 n NOx. Concentraia
medie a amoniacului n atmosfer se estimeaz la 2,5-3 mkg/m3 [2, 5, 13].
Agresivitatea coroziv a atmosferei este provocat i de formarea smogului
fotochimic. Oxizii CO, NO, NO2 i hidrocarburile sub aciunea radiaiei solare favorizeaz
formarea ozonului [5].
Un ciclu tipic de reacii la formarea smogului fotochimic este urmtorul:
Reacii primare:
2NO + O2 2NO2;
NO2 h NO + Oo;
R-COH h Ro + HCOo.
Reacii secundare:
Oo + O2 O3;
O3 + NO NO2 + O2;
NO2 + O2 h NO + O3;
O3 + olefine Ro, ROo, RCOo, ROOHo, polymeri;
Ro + O2 ROOo;
RCOo + O2 RCOOOo.
Aceste reacii nu iau n consideraie multiplele produse chimice caracteristice proceselor
din chimia organic. De exemplu, degajarea stirenului, halogenilor, clorului, bromului
care sub influena reaciilor fotochimice, trec uor n stare excitat [2, 5, 12].
Unele reacii duc la formarea radicalilor liberi, la eliberarea hidrogenului din
substanele organice n reaciile secundare cu radicalul Oo i ozonul O3. Radicali liberi se
formeaz i la descompunerea fotochimic a nitriilor i peroxinitriilor formai la etapele
iniiale.
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1.5
propilena
NO2
NO
RCOH
ozon
PAN
0.5
0
0
25
50
75
100
12 5
150
-0.5
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Nr. de
precipitaii
9
49
93
65
43
54
60
58
82
69
64
46
88
82
92
59
Nr. de mostre
colectate
43
152
272
177
174
125
306
148
253
192
183
59
108
124
116
65
pH mediu anual
6,71
6,11
5,97
5,70
5,21
5,45
6,60
5,34
4,89
5,97
5,26
6,53
6,02
5,28
6,20
Intervalul
valorii pH/an
2,65-7,60
3,51-9,13
3,80-10,35
3,75-9,70
4,20-7,85
2,55-7,30
4,10-7,85
4,40-8,22
3,00-6,80
4,00-6,50
5,00-6,50
3,8-6,00
4,00-8,40
4,20-7,20
3,90-8,40
4,60-8,30
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pH
[SO42-]
[HCO3-]
[Cl-]
[Ca2++ Mg2+]
[NH4+]
11.08.
1993
2
2
4
2
5
5
10
7
6,68
6,17
5,95
2,65
10,35
9,62
8,73
7,12
0,61
0,27
0,50
16,10
3,18
0,94
0,02
0,27
0,44
0,30
0,40
0,00
1,68
1,18
0,37
0,63
0,10
0,09
0,10
0,10
2,45
1,76
0,64
1,05
0,41
0,47
0,22
0,54
4,43
2,58
1,01
2,41
0,09
0,11
0,08
0,12
0,0
0,0
0,0
0,0
15.07.
1995
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Valorile medii anuale ale pH-ului n perioada de cercetare se nscriu n limitele 5,216,71,
deci practic neutre, dar dac analizm aciditatea mostrelor discrete vedem c pn n
anul 1998 crete procentul mostrelor de precipitaii acide, n anul 1999 brusc crete
procentul mostrelor bazice i neutre, dup care se observ o cretere neuniform a
numrului mostrelor acide. n anii 2000 i 2001 valoarea pH < 5,60 au avut 35,1% i
60% din mostre; pH 5,61-6,50 au avut 29,5% i 39,1%; pH > 6,50 au avut 35,4% i
0.9% corespunztor. n anul 2002 toate precipitaiile monitorizate au fost acide (Tabelul
3).
Tabelul 3
Repartizarea n (%) a mostrelor de ap din precipitaiile atmosferice dup valoarea pH-ului
pH/anul
1976-1995
1994
1995
1996
1997
1998
1999
<5.60
5.61-6.50
6.51-7.50
>7.51
34.0
35.0
21.0
10.0
22,4
26,0
30,0
21,3
24,0
43,0
19,6
13,4
70.0
25.0
3.0
2.0
43.7
36.8
16.6
2.9
68.8
27.2
4.0
0.0
33.0
50.0
16.0
1.0
pH/anul
2000
35.1
29.5
28.4
7.0
2001
60,0
39,1
0,0
0,9
2002
78,15
21,85
0,0
0,0
2004
83
17
0,0
0,0
2006
14,8
37
25,9
22,3
2007
29
49,2
16,2
5,6
2008
51
36,1
9,5
3,4
5.60
5.61-6.50
6.51-7.50
7.51
pH
SO2=
ClHCO3Ca2++Mg2+
NH4+
N
4.80
1.58
0.37
1.17
0.84
0.307
NE
5.51
0.16
0.16
0.48
0.51
0.042
E
5.44
1.06
0.40
0.90
0.83
0.193
SE
5.43
0.97
0.56
2.03
1.06
0.170
S
5.20
0.19
0.12
0.32
0.29
0.0
SW
5.46
1.07
0.63
0.98
0.71
0.140
W
5.53
0.82
1.11
3.23
2.34
0.0
NW
5.20
0.70
0.36
1.24
2.07
0.279
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impact i protecie. Informaie de sintez I.C..I.T.E. al R.M. Chiinu, 89 pp.
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tiinifice, 8-10 oct, Rmnicul Vlcea, Cciulata, Vol. II. pp. 919-922.
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nconjutor 2:27-29.
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varying pH and humic content. Environ. Pollut. 78(1-3):103-106.
[11] *** Legislaia de mediu a Republicii Moldova. http://www.mediu.md.
[12] Nicorici T., Buburuz D., Zacasovscaia R., 2003 Variaia pH-ului precipitaiilor n RM.
Environment & Progress, pp. 365-367.
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Pollut. 85(1):1-4.
[14] Rojanschi V., 1991 Posibiliti de evaluare global a impactului polurii asupra
calitii ecosistemelor. Mediul nconjurtor 2(1-2):45-52.
[15] erban R., State G., Petroaica B., 1993 Aspecte privind incidena ploilor acide n
Romnia. Mediul nconjurtor 4(3):39-45.
Autori:
Dionisie Buburuz, Institutul de Ecologie i Geografie al Academiei de tiine al Republicii Moldova, Str.
Academiei, nr. 1, Chiinu, Republica Moldova, MD 2028, e-mail: fordinu2000@yahoo.com; fordinu@mail.ru
Lilia Columbina, Universitatea T. G. evcenco, Tiraspol, Republica Moldova
Cum se citeaz acest articol:
Buburuz D., Columbina L., 2012 Precipitaiile acide i analiza fenomenului n contextul conveniilor
internaionale de mediu. Ecoterra 31:15-23.
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