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Global budget of major nitrification inhibitors (1980~2015)
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Yong Zhang (yongzhang.eco@outlook.com)1, Diego Abalos (d.abalos@agro.au.dk)2,
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Xiaoli Cheng (xlcheng@ynu.edu.cn)1,3*
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School of Ecology and Environmental Science, Yunnan University, Kunming, China
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2
Department of Agroecology, Land-CRAFT, Aarhus University, Tjele, Denmark
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3
Yunnan Key Laboratory of Soil Erosion Prevention and Green Development, Yunnan
Ministry of Education Key Laboratory for Transboundary Ecosecurity of Southwest China,
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University, Kunming, China
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*
Corresponding author. Email: xlcheng@ynu.edu.cn
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ORCID:
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Yong Zhang, https://orcid.org/0000-0002-1181-032X
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Diego Abalos, https://orcid.org/0000-0002-4189-5563
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Xiaoli Cheng, https://orcid.org/0000-0002-0346-675X
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The three most important nitrification inhibitors (NIs) applied worldwide are
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Dicyandiamide (DCD), 3,4-Dimethylpyrazole-phosphate (DMPP), and 2-Chloro-6-
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(trichloromethyl)-pyridine (Nitrapyrin) [1,2]. To assess the environmental fate of these
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NIs, a top-down model was developed to make a rough estimate of their global budget:
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𝑌𝑗,𝑡 = ∑ 𝑁𝑡 ⋅ 𝐴𝑡 ⋅ 𝐵𝑖,𝑡 ⋅ (𝑊𝑖 ± 𝜀𝑖 ) ⋅ 𝐹𝑖,𝑗,𝑡 ⋅ 1000
𝑖=1
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where i, j, and t denote the species of NIs use (i = 1 to 3; i.e., DCD, DMPP, and
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Nitrapyrin), the composition of NIs budget (j = 1 to 3; i.e., transport/degradation in
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biosphere, residue in soil, and leaching/runoff from soil), and the year (t = 1980 to 2015),
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respectively. Yj,t indicates the annual budget (Gg) of j. Other symbols: Nt, the amount
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(Tg) of N-fertilizers application; At, the percent (mass %) of N-fertilizers containing NIs;
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Bi,t, the share (mass %) of each NI use; Wi, the mixing ratio (mass %) of each NI to N-
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fertilizers; εi, the standard deviation (mass %) of Wi; Fi,j,t, the fraction (mass %) of
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different NI-flows for i. Please see details on the parameters in Tables 1~4. The results for
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global budget of major NIs (1980~2015) have been showed in Figure 1.
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Table 1. The percent of nitrogen (N) fertilizers containing nitrification inhibitors (NIs).
Percent (%) of N-fertilizers
Code
Query
Number of records
N-fertilizers
#1
192,958
NA
NIs
#2
5,497
2.85
containing NIs
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Notes: The percent of N-fertilizers containing NIs was estimated by the observation-
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based occurrences approach (according to probability theory), which is commonly used
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for global biodiversity estimations [3-6]. The literature search was performed at the Web
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of Science (2023-12-18) by using the following search terms:
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Query #1: TS = ("nitrogen" AND "fertili*") and Preprint Citation Index (Exclude – Database)
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Query #2: TS = (“nitrification” AND “inhibitor*”) and Preprint Citation Index (Exclude – Database)
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Table 2. The share of each nitrification inhibitor (NI) use.
Number of
Share (%) of each
records
NI use
#1
9,743
61.62
DMPP
#2
1,883
11.91
Nitrapyrin
#3
508
3.21
Others
(#5) NOT (#6)
3,678
23.26
All
DCD + DMPP + Nitrapyrin + Others
15,812
100
Code
Query
DCD
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Notes: We focused on three major NIs worldwide: Dicyandiamide (DCD), 3,4-
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Dimethylpyrazole-phosphate (DMPP), and 2-Chloro-6-(trichloromethyl)-pyridine
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(Nitrapyrin) [1,2]. The share of each NI use was estimated by the observation-based
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occurrences approach (according to probability theory), which is commonly used for
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global biodiversity estimations [3-6]. The literature search was performed at the Web of
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Science (2023-12-18) by using the following search terms:
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Query #1: TS = (“dicyandiamide”) and Preprint Citation Index (Exclude – Database)
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Query #2: TS = (“DMPP”) and Preprint Citation Index (Exclude – Database)
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Query #3: TS = (“nitrapyrin”) and Preprint Citation Index (Exclude – Database)
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Query #4: TS = (“nitrification” AND “inhibitor*”) and Preprint Citation Index (Exclude – Database)
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Query #5: #1 OR #2 OR #3 OR #4 and Preprint Citation Index (Exclude – Database)
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Query #6: #1 OR #2 OR #3 and Preprint Citation Index (Exclude – Database)
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Table 3. The parameters used for nitrification inhibitors (NIs) in the top-down model.
Fraction of different NI-flows
Percent of NSpecies of
fertilizers
NIs use
containing NIs
(A)
Share of
each NI use
(B)
Mixing ratio
(F) after 30 days of NIs use
of each NI to
Transport and
N-fertilizers
degradation in
(W)
biosphere
(j = 1)
Unit
Residue
in soil
(j = 2)
Leaching
and runoff
from soil
(j = 3)
mass %
DCD
61.62
3.4 ± 1.1
48.7
44.3
7.0
(i = 1)
(Table 2)
[7]
[ 8]
[ 8]
[ 9]
DMPP
2.85
11.91
1.2 ± 0.4
69.8
30.2
0
(i = 2)
(Table 1)
(Table 2)
[7]
[10]
[10]
[11]
Nitrapyrin
3.21
0.65 ± 0.15
85.7
14.3
0
(i = 3)
(Table 2)
[12]
[13]
[13]
[11]
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Notes: Where i and j denote the species of NIs use (i = 1 to 3; i.e., DCD, DMPP, and
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Nitrapyrin), and the composition of NIs budget (j = 1 to 3; i.e., transport/degradation in
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biosphere, residue in soil, and leaching/runoff from soil), respectively. DCD,
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Dicyandiamide; DMPP, 3,4-Dimethylpyrazole-phosphate; Nitrapyrin, 2-Chloro-6-
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(trichloromethyl)-pyridine. To be comparable for the test data of different NIs, we
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specified the test duration (i.e., 30 days, because this value is available for test
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experiments of DCD, DMPP, and Nitrapyrin [8,10,13]). The fraction of different NI-flows
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(after 30 days of NIs use) was estimated by experimental test data based on
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recommended doses for DCD (15.4 mg kg soil-1) [8], DMPP (1.54 mg kg soil-1) [10], and
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Nitrapyrin (2 mg kg soil-1) [2,13]. The DCD was subject to leaching/runoff (7%) [9,14]
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while no leaching/runoff of DMPP and Nitrapyrin was observed in lysimeter experiments
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[11], thus the leaching/runoff for DMPP and Nitrapyrin was set to 0.
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Table 4. The parameters used for nitrogen (N) fertilizers [15] in the top-down model.
Year
Amount of N-fertilizers application
Year
Amount of N-fertilizers application
(t; unit: yr)
(N; unit: Tg)
(t; unit: yr)
(N; unit: Tg)
1980
95.33
1998
127.81
1981
96.24
1999
129.74
1982
97.23
2000
126.66
1983
101.54
2001
128.84
1984
106.95
2002
130.02
1985
107.90
2003
135.96
1986
109.72
2004
138.50
1987
113.54
2005
141.45
1988
117.75
2006
143.09
1989
118.57
2007
148.05
1990
117.15
2008
149.46
1991
116.13
2009
151.84
1992
114.60
2010
158.70
1993
113.07
2011
161.71
1994
115.10
2012
167.88
1995
121.14
2013
173.48
1996
125.56
2014
177.30
1997
125.10
2015
178.50
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Notes: The three nitrification inhibitors (DCD, DMPP, and Nitrapyrin) were registered
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for use before 1980s [2], thus data on global use of N-fertilizers after 1980 were selected
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to match that on nitrification inhibitors. DCD, Dicyandiamide; DMPP, 3,4-
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Dimethylpyrazole-phosphate; Nitrapyrin, 2-Chloro-6-(trichloromethyl)-pyridine.
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Table 5. Experimental evidences for side-effects of major synthetic nitrification inhibitors (SNIs).
SNIs
Side-effects on
Description
Refer
ence
“However, the use of nitrification inhibitors is not free of side-effects. Some may be absorbed by the plant and
cause phytotoxicity or even affect the food chain”.
Plants
“The use of high DCD concentrations affected the leaf chlorophyll content and plant growth”.
“The action of dicyandiamide is found to be toxic to germination of seed in beans and of growth generally in
other plants such as flax”.
“DCD decreased plant dry weight and leaf chlorophyll concentration”.
DCD
[16]
[17]
[18]
“Dicyandiamide (DCD), considered to be a nitrification inhibitor, poses threat to human’s health with exposure
from milk, infant formula and other food products”.
Animals
[19]
“The pepsin interacted with DCD at a hydrophobic cavity, leading to a conformational changes in the pepsin”.
“Multisystemic granulomatous and haemorrhagic syndrome resembling cell-mediated hypersensitivity,
associated with DCD ingestion”.
[20]
“DMPP translocates to leaves and high doses may cause visual phytotoxicity symptoms”.
Plants
“When DMPP accumulates in leaves it induces stress responses, notably provoking changes in cell redox
[21]
balance, hormone signaling, protein synthesis and turnover and carbon and nitrogen metabolism”.
“DMPP only provoked detrimental effects in plants at very high dose”.
[22]
“DMPP, DMOP, and DMMP commonly inhibited the total reproduction while stimulated lifespan”.
“DMPP, DMOP, and DMMP caused different regulations on the expressions of vab-1, ceh-18, and gsa-1 which
DMPP
are involved in oocyte growth, ovulation, and maturation. Meanwhile, they commonly downregulated those of
Animals
[23]
rme-2 and rcy-4 that regulate germ cells and gonads and lipid metabolism in oocytes”.
“Reproductive toxicities of DMPs depended on the exposure life stages and also the chemical structures”.
“Exposure to DMPP caused the lethality at the L2/L3 molt, and this toxicity was concentration-dependent”.
“These observations imply the potential sensitivity of L2/L3 molting time to certain environmental toxicants or
stresses in nematodes”.
[24]
Microbes
“DMPP application increased the number of colony forming units of various fungi (off-target microbes)”.
[25]
“DMPP imposed significant changes in the composition of fungal communities (off-target microbes)”.
[10]
“Nitrapyrin toxicity appeared as a curling of leaf margin and a tendril type of stem growth”.
“Toxicity of Nitrapyrin to sunflower under different N nutrition regimes”.
Plants
Nitrapyrin
“Nitrapyrin toxicity appeared as leaf chlorosis in cow peas, and interveinal chlorosis in chick peas”.
“A suppression in plant growth was associated with Nitrapyrin application”.
Microbes
[27]
“Visual symptoms of Nitrapyrin toxicity appeared as leaf curling and tendril type of stem growth”.
[28]
“According to Nitrapyrin labels, it has an acute toxicity to aquatic invertebrates and algae/aquatic plants”.
[29]
“Therefore, the data support the conclusion that Nitrapyrin-induced liver tumors in female mice are mediated
Animals
[26]
via a CAR MoA”.
[30]
“According to Nitrapyrin labels, it has an acute and chronic toxicity to fish”.
[29]
“Nitrapyrin inhibited growth, CH4 oxidation (involved in off-target microbes)”.
[31]
“Piadin and Vizura (two commercial NIs) showed ecotoxic effects throughout all experiments”.
Plants
Microbes
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[32]
species L. gibba and on the root development of several terrestrial plant species”.
Others
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“All findings indicate ecotoxic effects of Piadin and Vizura (two commercial NIs), especially on the aquatic
“QI (quinone imine, a derivate from ethoxyquin) induced significant changes (off-target microbes) in the
composition of the bacterial and fungal communities”.
[33]
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Figure 1. Global budget of major NIs (after 30 days of NIs use). Shading area indicates
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standard deviations of top-down estimated NI-flows.
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