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ODESSA NATIONAL I. I. MECHNIKOV UNIVERSITY
Regional Monitoring Centre for Integrated Environmental Monitoring
Nitrogen monitoring activities
in support of the Black Sea convention
TFRN-10, Lisbon, 29th-30th April 2015
Medinets S., Kotogura S., Pitsyk V., Mileva A., Snigirov S.,
and Medinets V.
Location of measurement activities of ONU
in the Dniester and the Black Sea Basins
TFRN-10, Lisbon, 29th-30th April 2015
Activity
NW
Bla
ck S
ea
Established in 2001
Multitask full-time integrated monitoring station (except January-March period):
a) hydrological measurements
b) atmospheric chemistry
c) sea chemistry
d) ground water chemistry
e) phytoplankton study
f) sea microbiology study
g) chlorophyll
h) meteorological observations
i) ichthyology study
j) geological and geo-engineering study
k) soil study
l) biological studies (ornithology, botany etc)
N related investigations:
a) atmospheric N bulk and wet deposition (NH4+, NO3
-, NO2- and organic N)
b) sea water monitoring of NH4+, NO3
-, NO2- and organic N concentrations
c) ground water N species concentrations
The Zmiiniy Island station [ZMN]
TFRN-10, Lisbon, 29th-30th April 2015
-100 -75 -50 -25 0 25 50 75 100
Sea-origin
NO3-(N)
NH4+(N)
NO2-(N)
PO43-(P)Dry Wet
Findings
NW
Bla
ck S
ea
The Zmiinyi Island station [ZMN]
Atmospheric N deposition (Medinets & Medinets, 2012)
For NH4+ both dry (51%) and wet (49%) ways of removing were important
For NO3- wet scavenging seems to be the prevalent one (59%)
Dry sedimentation was more important for PO43- (76%) than washing-out with rain
Strong correlation between amount of precipitation and wet deposited NO3- (r=0.67;
p < 0.001) has been found
For dry deposited NH4+ strong correlation with NO3
- (r=0.59) and PO43- (r=0.77) at p<0.001 was
registered
77% 23%
74% 26%
51% 49%
41% 59%
70-79% 21-30%
Fig. 4. Average input (%) of dry and wet deposition for certain ions (2004 – 2010)
TFRN-10, Lisbon, 29th-30th April 2015
Findings
NW
Bla
ck S
ea
The Zmiinyi Island station [ZMN]
Atmospheric N deposition (Medinets & Medinets, 2010, 2012)
Fig. 5. Continental origin N and P input to bulk
deposition
0
300
600
900
1200
1500
Region of the
Zmeiny Island
(2008-2010)
Region of the
Zmeiny Island
(2003-2007)
North-Western
Black Sea (1990-
1992)
kg
km
-2 y
ear-1
NH4+(N) NO3-(N) PO43-(P)
For bulk deposition around 99%
NH4+ and NO3
- as well as 91-98%
PO43- are transported to sea
surface layer of atmosphere from
continental natural and
anthropogenic sources
TFRN-10, Lisbon, 29th-30th April 2015
Findings
NW
Bla
ck S
ea
The Zmiiniy Island station [ZMN]
Atmospheric N deposition (Medinets, 2014)
Fig. 6. Monthly mean bulk N deposition (by constituents) and
precipitation
Total organic N content in deposition was dominant in most cases and its contribution
varied in ranges of 18.8-95.4%
Jun Jul Aug Sep Oct Nov DecMay
TFRN-10, Lisbon, 29th-30th April 2015
Findings
NW
Bla
ck S
ea
The Zmiiniy Island station [ZMN]
Atmospheric N deposition (Medinets et al., 2014; Medinets, 2014)
Fig. 7. Annual atmospheric N deposition
Average share of TON (2011-2012) was ca. 66% (1777±678 kg N km-2 year-1)
0
500
1000
1500
2000
2500
3000
2011 2012
Dep
os
itio
n r
ate
, k
g N
km
-2y
-1
NO3-
NH4+
TON
Average TN deposition was 2684±316 kg N km-2 y-1
TFRN-10, Lisbon, 29th-30th April 2015
Findings
NW
Bla
ck S
ea
The Zmiiniy Island station [ZMN]
Atmospheric N deposition (Medinets et al, 2014; Medinets, 2014)
Water soluble and water insoluble organic were found to be approximately
equally distributed in this period
0
20
40
60
80
100
1 2
Co
nte
nt
of
N s
pe
cie
s, %
NO3-
NH4+
WSON
WITN (PON)
Fig. 8. Contribution of N species into atmospheric N deposition in Jul – Dec 2012
28.3%
24.4%
28.7%
18.6%
TFRN-10, Lisbon, 29th-30th April 2015
The Black Sea N budget
Bla
ck s
ea
Fig. 3. Mass balance of N (Gg N y-1) for the Black Sea (Medinets, 2014)
Output768-1692
TFRN-10, Lisbon, 29th-30th April 2015
Activity
Cro
pla
nd
in
th
e D
nie
ster
ba
sin
Established in 2006 under NitroEurope IP
Following investigations have been performed/-ing:
a) air concentration of gases (incl. NH3, HNO3) and aerosols (incl. NH4+, NO3
-)
b) meteorological observations
c) CO2, H2O and heat fluxes
d) soil N2O and CH4 fluxes (2009-2010)
e) NH3 fluxes (2009-2010)
f) atmospheric bulk deposition (incl. NH4+, NO3
-, NO2- , WSON, WISON)
g) soil analysis (2006-2012) and incubation experiments (2006-2010)
h) biomass C/N (2008-2009)
i) management data collection (fertilization, irrigation, tillage etc)
j) soil NO/NO2 fluxes (2012-2014)
k) NO, NO2, O3 concentration measurements (2012-2014)
l) O3 fluxes (2012-2014)
m) LAI (2012-2014)
n) leaf wetness (2012-2014)
The Petrodolinskoe monitoring station [PTR]
TFRN-10, Lisbon, 29th-30th April 2015
Polymers
(e.g. proteins)
Monomers
(e.g. amino acids)
Organic
fertilisersMineral
fertilisers
Microbes
NH3
NH4+
NO2-
NO3-
NO N2O N2
Plantsoil
atmosphere
(Medinets, unpublished)
DNRA
Anammox
Denitrification
(heterotrophic)
BNF
Dead SOM Depoly-
merization
Microbial
immobilization
Ammoni-
fication
Microbes
death
Leaching
Root
exudation
Dead leaves
and branches
Nitrification
N2N2O
NO2
+O3
+NO3.
HNO3 +OH-
NO
NO3- Uptake aerosol
& NH3 reaction
NH3
NH4+
Roots
Canopy
Dead plant
rootsVolatilisation
Organic N
Fertilization
Acid gases &
aerosol reactions
+ CHOH
+CH3C(O)OO
+CH3C(O)OO via HNO radical formation
+hv
+hv
+thermal decomposition
Denitrification
(nitrifier)
Simplified N cycle in terrestrial ecosystems
(e. g. PAN’s)(e. g. H-CN,
CH3-CN)
Uptake by plant
Release by plant
Fertilization
Leaching
Usually not significant
General
Info
Findings
Low N2О emissions have been found
Nitrous oxide fluxes were small, and responded positively to rainfall (r = 0,51; p <
0,07)
Monthly N2О flux, precipitation and tillage (Medinets et al., 2011)
Fertilizer induced emissions were considerably smaller (0.27 %) than the IPCC
default emission factor 1 % (IPCC, 2006)
-40
0
40
80
120
160
Se
p-0
9
Oc
t-0
9
No
v-0
9
De
c-0
9
Ja
n-1
0
Fe
b-1
0
Ma
r-1
0
Ap
r-1
0
Ma
y-1
0
Ju
n-1
0
Ju
l-1
0
Au
g-1
0
Se
p-1
0
Oc
t-1
0
No
v-1
0
De
c-1
0
N2O
(g
N h
a-1
mo
nth
-1)
0
20
40
60
80
100
Fe
rt. (k
g N
ha
-1)
/ T
illa
ge
(c
m)
/
Pre
cip
ita
tio
n (
mm
)
N2O Fertiliser input Tillage Precipitation
N2O
Annual N2О budget was 215±123 g N ha-1 in 2010 (winter wheat)
The Petrodolinskoe monitoring station [PTR]
TFRN-10, Lisbon, 29th-30th April 2015
Findings
Annual estimated NH3 budget was -160±322 g N ha-1 y-1
-250
-175
-100
-25
50
125
200
275
350
Ju
l-09
Au
g-0
9
Sep
-09
Oct-
09
No
v-0
9
Dec'0
9
Jan
-10
Feb
-10
Mar-
10
Ap
r-10
May-1
0
Ju
n-1
0
Ju
l-10
Au
g-1
0
Sep
-10
Oct-
10
No
v-1
0
Dec-1
0
Flu
x, g N
ha
-1 m
onth
-1
Monthly NH3 fluxes in 2009 – 2010 (Medinets et al., 2011)
NH
3
Mean total mineral N concentration in ambient air (in gaseous forms of HNO3,
HNO2, NH3) was 2.32±1.35 μg N m-3 in 2007 - 2010
Air gaseous and aerosols N concentration (figures not shown)
Mean total mineral N concentration in ambient air (in aerosols forms of NO3-, NO2
-,
NH4+) was 1.89±1.62 μg N m-3 in 2007 - 2010
The Petrodolinskoe monitoring station [PTR]
TFRN-10, Lisbon, 29th-30th April 2015
Findingsplo
ughin
g [
40 c
m]
har
row
ing [
15 c
m]
sow
ing [
5 c
m]
dri
ppin
g i
nst
. [1
0 c
m]
cult
ivat
ion [
10cm
]
cutt
ing a
nd d
rip.
de-
inst
. [1
0 c
m]
dis
kin
g [
15cm
]
wit
h p
lant
resi
dues
harvesting
dis
kin
g [
15 c
m]
plo
ughin
g [
40 c
m]
cult
ivat
ion [
10
-15 c
m]
dri
p.
de-
inst
. [1
0 c
m]
1st
and 2
nd
cult
ivat
ions
[10
-15 c
m]
37 days ofno rain period
Temperature rather than SMC has been identified as main abiotic triggering NO emission factor
We have found that dripping irrigation applications decrease NO emission (during the events)
We have demonstrated that N and K (during fertigation) has opposite effect on NO emission
Soil
NO
Soil NO fluxes (μg N m-2 h-1) during intensive measurement campaign in 2012-2014 (Medinets et al., in preparation)
The Petrodolinskoe monitoring station [PTR]
TFRN-10, Lisbon, 29th-30th April 2015
Activity
Dn
iest
er
Ba
sin
Started in 2010
Following investigations have been carrying out in 3 measurements sites:
a) atmospheric bulk deposition (incl. NH4+, NO3
-, NO2-, WSON, WISON)
b) hydrological observations (incl. pH, conductivity, TDS, temperature)
c) hydro-chemical investigations (incl. NH4+, NO3
-, NO2-, DON)
d) phytoplankton study
e) microbiology study
f) chlorophyll
The Dniester Basin measurements
TFRN-10, Lisbon, 29th-30th April 2015
Findings
Average annual deposition in 2011-2013:
11.4 kg N ha-1 for cropland site
11.4 kg N ha-1 for garden site
7.7 kg N ha-1 for natural site
N d
ep
osi
tion
Fig. 2. Annual deposition rates in cropland (a),
garden (b) and natural (c) sites
(c)
(b)
(a)cr
op
land
nat
ura
l
gar
den
The Dniester Basin measurements
Findings
N d
ep
osi
tion
Annual distribution of various N constituents in TN deposition in 2013 (Medinets et al., 2014)
The Dniester Basin measurements
TFRN-10, Lisbon, 29th-30th April 2015
Findings
Average annual N flow to the Dniester Estuary was 36.6±25.7 Gg N y-1
Flu
via
l N
flo
w
Annual riverine N flow to the Dniester Estuary (Medinets et al., 2015)
The Dniester Basin measurements
DON
TFRN-10, Lisbon, 29th-30th April 2015
Objectives
To prevent pollution by hazardous substances or matter [Annex]
To control* the pollution from land-based sources [Protocol]
To control* the pollution of the marine environment from vessels
To control* the pollution of the marine environment resulting from emergency situations [Protocol]
To control* the pollution by dumping [Protocol]
To control* the pollution caused by or connected with activities on the continental shelf
To control* the pollution from or through the atmosphere
To protect the biodiversity and the marine living resources
To prevent the pollution from hazardous wastes in transboundary movement and the illegal traffic there of
To provide framework for scientific and technical co-operation and monitoring activities.
*’to control’ means also ‘to prevent’ and ‘to reduce’
The Black Sea Convention
TFRN-10, Lisbon, 29th-30th April 2015
Thank you for your attention!