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Summary
The onset of the colony collapse disorder (CCD) in 2006 has been devastating
to the bee industry because the wintertime reduction in honeybees threatens the US
and global food supply. In this work, it is proposed that atmospheric carbamates
produced from available ground-level ammonia and carbon dioxide can lead to the
honeybee colony collapse disorder (CCD) effect. Carbamates are known powerful
insecticides so their production, if verified by field measurement and further
modeling, can lead to this condition. Using a computed carbamate insecticide LD50
value of 31.7 ppmm from the literature for similar carbamates, it is shown that the
computed wintertime carbamic acid concentration is 480 ppmm at an urban site in
northern India (Hisar), hence toxic to the honeybee. An estimate of the seasonal
effect in carbamic acid concentration based on temperature leads to an reduction by
a factor of 3000 the summertime estimated value, which for the India site during
summer is only 0.2 ppmm, hence non-lethal to the honeybee. Atmospheric
deposition into the bees food source, nectar, and other exposure such as pollen may
explain the CCD effect.
Keywords
Colony collapse disorder; toxicity; atmospheric carbamates; lethal dose.
Short Title
Atmospheric carbamates as a cause of bee colony collapse
1. Introduction
An emerging crisis recently has been the honeybee colony collapse disorder
(CCD) phenomena. There have been significant reductions, known to be seasonal, in
the domestic honeybee populations that the world relies upon for our food supply
as they support approximately 80% of the agricultural pollination capacity [1].
Despite detailed laboratory studies that indicate that honeybees that have died by
CCD carry in vivo pesticides, herbicides, and fungicides, the same is true of healthy
bees that have been analyzed [1].
Other possibilities for CCD include viral or bacterial infections. However, in
France where bees were analyzed to be infected, even when the infections were
reduced their bee populations still continue to decline [1]. The evidence implies that
this effect is unlikely (but still possible with other viral/bacterial strains).
A third possibility includes the effects of global climate change. This allencompassing topic is also likely, especially as is discussed here in terms of a trend
observed in one particular atmospheric pollutant, carbamates. Carbamates are
amino-carboxylate entities and a powerful class of insecticides [2,3], making their
atmospheric production particularly of concern as a cause of the CCD effect.
Carbamates are formed in the atmosphere, as is hypothesized here, by the reaction
of amines (e.g., ammonia) with carbon dioxide, that is facile under ambient
temperature conditions at high concentrations [4]. In this work, the high
concentration carbamate formation literature [4] is used to extrapolate carbamate
production under atmospheric conditions. The onset of CCD in about 2005 can be
correlated with the global distribution of ammonia and carbon dioxide considering
yearly trends, their seasonal variation, and geographic location, and can be used to
assert an explanation for the CCD effect. In this effort, reliance upon atmospheric
chemistry and insect (i.e., honeybee) toxicology [5,6] is utilized to develop a
hypothesis of CCD causation by atmospheric-derived carbamates.
There are certain characteristics associated with the CCD phenomenon that
suggest the honeybees are dying by atmospheric pollutant(s) [1]. In California, there
is a dramatic effect between healthy bee populations in summer, to bee attrition in
winter months. This seasonal change occurs every year beginning with the onset of
CCD. The troposphere in winter also experiences a dramatic decrease in actinic flux,
where a shift from a more oxidizing to reducing atmosphere takes place from
summer to winter. One such atmospheric pollutant is the NOx to NHy partitioning
that occurs, particularly ammonia formation in winter. This is not the only trace gas
pollutant undergoing this change, and could be associated with CCD, but is the only
cause considered here. In Florida, one commercial beekeeper noted that
approximately 1/3 of his bees were functioning normally, another 1/3 lethargic, and
1/3 cannot leave hive and eventually die. This could be associated with
characteristics of the lethal dose (LD33, LD67, LD100, etc.). Finally, urban air masses
that influence (e.g., transport to) a region where bees reside also play a role in the
CCD phenomenon.
2
(1)
(2)
(3)
(4)
It is seen that the aqueous CA production is second order in NH3 because two amino
groups are present in the CA molecule. Similarly, the decomposition of CA occurs in
their experiment by reaction with CO2, yielding (where kd is positive)
d[CA]/dt = -kd [CA] [CO2(aq)].
(5)
Utilizing the data of Park et al. [4] using [CA]=[NH3]=5 wt.%, in their Figure 1 (for
[CA] formation) and Figure 3 ([CA] decay) they observed respective lifetimes of 30
min. and 323 min. This results in calculated rate coefficients at 5 wt.% reagents of
kf=1.33x10-3/%2-min, and kd=6.19x10-4/%-min. A unit conversion to ppmm yields
kf=1.33x10-11/ppmm2-min and kd=6.19x10-12/ppmm-min. Other units may be more
suitable to certain models.
A. Estimated Urban Equilibrium Atmospheric Carbamic Acid
Concentration A simplified scenario
For the estimation of CA, data from a typical rural site is utilized. This
estimate is based on work of Ram et al. based on ground field measurements in the
Indo-Gangetic plain Hisar site, in northern India [13]. From this work, the
concentration of NH4HCO3 can be written,
[NH4HCO3] wt.% = {(%,NH4HCO3)(WSIS(g/m3))/(TSP(g/m3))}
(6)
The values in eqn(6) from Ram et al. [12] at the Hisar site are the wt.% of inorganic
ammonium carbonate (i.e., 12%), the total atmospheric water-soluble inorganic
concentration (i.e., WSIS(g/m3)=45.6, and the total aerosol condensed phase
concentration (TSP(g/m3)=147). The result is [NH4HCO3(aq)]=4 wt.%. It is
important to note in this dataset the concentrations of [NH4+]=[HCO3-], so have been
grouped into the combined compound [NH4HCO3(aq)].
With a value of [HCO3-]=4 wt.%, an estimate of the aqueous CO2(aq), or its
equivalent carbonic acid, can be obtained from the equation,
H2CO3 <-> H+ + HCO3- .
(7)
The data from Table 3 is used to compute a reaction free energy of 36.3
kJ/mol [12]. Hence an equilibrium constant of K=4.3x10-7 is computed at 298 K. At
neutral pH=7, the concentration ratio [H2CO3]/[HCO3-]=0.23. Using the [HCO3-]=4
wt.% value results in the [H2CO3]=0.92 wt.% concentration. Finally, substitution into
eqn(3) above yields [CA]=0.05 wt.%=480 ppmm. Of significance is that this value
represents the urban, wintertime, concentration, and that 480 ppmm is greater than
the 31.7 ppmm value LD50 value toxic to the honeybee. Recall, it is observed that
primarily wintertime is more detrimental to bee health than summertime. Next, an
estimate of summertime carbamic acid concentration will be estimated.
An estimated summertime carbamic acid concentration can be estimated
based on the kinetic analysis above where the [CA] production is second order in
ammonia concentration. The question is then, what is the expected seasonal
variation in NH3 expected, as this value has not been measured? Assuming a typical
mid-latitude seasonal summer to winter temperature decrease of 25 Celcius,
together with the observation of a 2.2-fold increase in NH3 mixing ratio per 0.5
[11] Latimer WM, (1952) The oxidation states of the elements and their potentials in
aqueous solutions, Englewood Cliffs, NJ. 2nd Ed., Prentice-Hall Inc.
[12] Bard AJ, Parsons R, Jordan J, (1985) Standard potentials in aqueous solution,
Marcel Dekker Inc., New York.
[13] Ram K, Sarin MM, Sudheer AK, Rengarajan R, (2012) Carbonaceous and
Secondary Inorganic Aerosols during Wintertime Fog and Haze over Urban Sites in the
Indo-Gangetic Plain, Aerosol and Air Quality Research, 12, 359370.
[14] Van Damme M, Clarisse L, Heald CL, Hurtmans D, Ngadi Y, Clerbaux C, Dolman
AJ, Erisman JW, Coheur P-F, (2014) Global distributions, time series and error
characterization of atmospheric ammonia (NH3) from IASI satellite observations, Atmos.
Chem. Phys. 14(6), 2905-2922.
JMJ