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Cu-K␣ (␭ ⫽ 1.54184 Å) radiation, on a Bruker Smart 6000


A CCD system equipped with a rotating anode. The results
Zn(C5Me5)2 + Me3COH [Zn(OCMe3)2] x + 2C5Me5H of the two determinations are very similar. Data from
(excess) the second analysis can be obtained from the authors,
upon request.
B 14. A compound initially formulated as Co2(␩5-C5Me5)2 by
Zn2(η5-C5Me5)2 + Me3COH [Zn(OCMe3)2] x + Zn + 2C5Me5H J. J. Schneider, R. Goddard, S. Werner, and C. Krüger
(excess)
[Angew. Chem. Int. Ed. Engl. 30, 1124 (1991)] was
subsequently shown to be Co2(␩5-C5Me5)2(␮-H)320.
Fig. 4. Reactions of Zn(C5Me5)2 (A) and Zn2(␩5-C5Me5)2 (B) with Me3COH. 15. J. L. Kersten et al., Angew. Chem. Int. Ed. Engl. 31,
1341 (1992).
The alkoxide has been additionally identified 6. F. Rittner, A. Seidel, B. Boddenberg, Micropor. Meso- 16. P. Jutzi, N. Burford, Chem. Rev. 99, 969 (1999).
por. Mat. 24, 127 (1998). 17. L. Pauling, The Nature of the Chemical Bond (Cornell
by comparison of its infrared, 1H, and 13C{1H} Univ. Press, Ithaca, NY, ed. 3, 1960), chap. 7.
7. Y. Tian, G. D. Li, J. S. Chen, J. Am. Chem. Soc. 125,
NMR spectra with those of an authentic sample 6622 (2003). 18. E. Dorn, J. Chem. Soc. Chem. Commun. 1971, 466 (1971).
prepared from Zn(C2H5)2 and Me3COH (22). 8. P. O’Brien, in Comprehensive Organometallic Chem- 19. H. Hao et al., Chem. Commun. 2001, 1118 (2001),
The synthesis of compound 1 suggests istry II, G. Wilkinson, F. G. A. Stone, E. Abel, Eds. and references therein.
(Pergamon, Oxford, UK, 1995), vol. 3, chap. 4. 20. In this refinement, the data with large 2␪ angles were
that related complexes of Cd and Hg could 9. J. T. B. H. Jastrzebski, J. Boersma, G. van Koten, W. J. J. given higher weights, followed by a difference elec-
be isolated. It also seems plausible that the Smeets, A. L. Spek, Recl. Trav. Chim. Pays-Bas 107, tron density synthesis with reflections with sin␪/␭.
stabilization of the [Zn–Zn]2⫹ unit does not 263 (1988). 21. R. Han, I. B. Gorrell, A. G. Looney, G. Parkin, J. Chem.
10. R. Blom et al., Acta Chem. Scand. A 40, 113 (1986). Soc. Chem. Commun. 1991, 717 (1991).
require the existence of Zn–C bonds, which
11. Data were identified by x-ray powder diffraction. 22. G. E. Coates, P. D. Roberts, J. Chem. Soc. A 1967,
means that classical coordination com- 12. Materials and methods are available as supporting 1233 (1967).
pounds of the Zn22⫹ central unit are rea- material on Science Online. 23. In memoriam of Professor Roberto Fernández de
sonable targets for future synthetic and 13. Two x-ray crystallographic analyses were carried out. The Caleya. We thank A. Justo (x-ray powder diffraction),
first made use of Bruker-Siemens Smart 1K charge-cou- M. A. Avilés (Raman spectra), and R. Fernández for
structural studies. pled device (CCD) diffractometer with a graphite mono- their valuable help, and R. A. Andersen (University of
chromated Mo-K␣ (␭ ⫽ 0.71073 Å) radiation. Crystal data California, Berkeley) for obtaining the mass spectrum
References and Notes for 1 was as follows: C20H30Zn2; molecular weight ⫽ of compound 1. Supported by the Ministry of Science
1. F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Boch- 401.18; triclinic; space group P1; Z ⫽ 2; T 173 (⫾2) K; a ⫽ and Technology of Spain (to E.C., Project BQU2001-
mann, Advanced Inorganic Chemistry (Wiley, New 6.9329 (⫾3) Å, b ⫽ 10.8831 (⫾5) Å, c ⫽ 13.8384 (⫾7) Å, 1995; and to I.R. for a research studentship).
York, ed. 6, 1999), chap. 15. ␣ ⫽ 109.777 (⫾1)°, ␤ ⫽ 101.603 (⫾1)°, ␥ ⫽ 94.201
2. N. Wiberg, Ed., Holleman-Wiberg Inorganic Chemistry (⫾1)°, and V ⫽ 951.09 (⫾8) Å3; goodness of fit ⫽ 0.988; Supporting Online Material
(Academic Press, New York, ed. 34, 2001), chap. XXIII. R1[I ⬎ 2␴(I)] ⫽ 0.031; wR2 ⫽ 0.076 (all data). Atomic www.sciencemag.org/cgi/content/full/305/5687/1136/
3. R. Faggiani, R. J. Gillespie, J. E. Vekris, J. Chem. Soc. coordinates, bond lengths, and angles and other important DC1
Chem. Commun. 1986, 517 (1986). parameters have been deposited with the Cambridge Materials and Methods
4. D. L. Reger, S. S. Mason, J. Am. Chem. Soc. 115, Crystallographic Data Centre as supplementary publication Tables S1 to S4
10406 (1993). CCDC 233010. Details of the x-ray crystallographic anal- References
5. D. H. Kerridge, S. A. Tariq, J. Chem. Soc. A 1967, 1122 ysis are also available on Science Online. The second anal-
(1967). ysis was carried out at –173°C (100 K), with the use of 14 June 2004; accepted 7 July 2004

Regions of Strong Coupling Between The critical importance of the ocean


surface in this regard is well known (1).

Soil Moisture and Precipitation Ocean temperature anomalies can be pre-


dicted a year or more in advance (2).
Furthermore, the atmosphere responds par-
The GLACE Team: Randal D. Koster,1* Paul A. Dirmeyer,2 ticularly strongly (and predictably) to
Zhichang Guo,2 Gordon Bonan,3 Edmond Chan,4 Peter Cox,5 C. T. ocean temperature anomalies in certain re-
Gordon,6 Shinjiro Kanae,7 Eva Kowalczyk,8 David Lawrence,9 gions—in “hot spots” of ocean-atmosphere
Ping Liu,10 Cheng-Hsuan Lu,11 Sergey Malyshev,12 coupling. The eastern equatorial Pacific is
Bryant McAvaney,13 Ken Mitchell,11 David Mocko,10
1
NASA Goddard Space Flight Center, Greenbelt, MD
Taikan Oki,14 Keith Oleson,3 Andrew Pitman,15 Y. C. Sud,1 20771, USA. 2Center for Ocean-Land-Atmosphere
Christopher M. Taylor,16 Diana Verseghy,4 Ratko Vasic,17 Studies, Calverton, MD 20705, USA. 3National Center
Yongkang Xue,17 Tomohito Yamada14 for Atmospheric Research, Boulder, CO 80307, USA.
4
Meteorological Service of Canada, Toronto, Ontario
M34 5T4, Canada. 5Hadley Centre for Climate Predic-
Previous estimates of land-atmosphere interaction (the impact of soil moisture on tion and Research, Exeter EX1 3PB, UK. 6Geophysical
precipitation) have been limited by a lack of observational data and by the model Fluid Dynamics Laboratory, Princeton, NJ 08542, USA.
7
Research Institute for Humanity and Nature, Kyoto
dependence of computational estimates. To counter the second limitation, a dozen 602-0878, Japan. 8CSIRO Atmospheric Research, As-
climate-modeling groups have recently performed the same highly controlled pendale, Victoria 3195, Australia. 9University of Read-
numerical experiment as part of a coordinated comparison project. This allows a ing, Reading, Berkshire RG6 6BB, UK. 10Science Appli-
multimodel estimation of the regions on Earth where precipitation is affected by cations International Corporation, Beltsville, MD
20705, USA. 11National Center for Environmental
soil moisture anomalies during Northern Hemisphere summer. Potential benefits Prediction, Camps Springs, MD 20746, USA. 12Prince-
of this estimation may include improved seasonal rainfall forecasts. ton University, Princeton, NJ 08544, USA. 13Bureau of
Meteorology Research Centre, Melbourne, Victoria
Atmospheric chaos severely limits the to slowly varying states of the ocean and 3001, Australia. 14University of Tokyo, Tokyo 153-
predictability of precipitation on seasonal land surface— components of the Earth 8505, Japan. 15Macquarie University, North Ryde,
New South Wales 2109, Australia. 16Centre for Ecol-
time scales. Weather forecasts, which rely system that can be predicted weeks to ogy and Hydrology, Wallingford, Oxfordshire OX10
heavily on atmospheric initialization, rarely months in advance. A systematic response 8BB, UK. 17University of California, Los Angeles, CA
demonstrate skill beyond about a week. of the atmosphere to these boundary 90095, USA.
Hope for accurate seasonal forecasts lies components would contribute skill to *To whom correspondence should be addressed. E-
with simulating the atmospheric response seasonal prediction. mail: randal.d.koster@nasa.gov

1138 20 AUGUST 2004 VOL 305 SCIENCE www.sciencemag.org


REPORTS
the most famous oceanic hot spot, playing a ditions affect some atmospheric quantity Hot spots appear in the central Great Plains of
key role in the El Niño–La Niña cycle (3). X— can be estimated (18) for each of the two North America, the Sahel, equatorial Africa,
Another potentially useful slowly varying ensembles with the diagnostic ⍀: and India. Less intense hot spots appear in
component of the Earth system is soil mois- ⍀ ⫽ (16␴2⬍X⬎ – ␴2X )/15␴2X (1) South America, central Asia, and China.
ture, which can influence weather through its The positions of the hot spots are not
impact on evaporation and other surface en- where ␴ X is the intraensemble variance of X
2
unexpected (8, 21), particularly if the soil
ergy fluxes. Soil moisture anomalies can per- and ␴2⬍X⬎ is the corresponding variance of moisture influence is presumed to be local
sist for months (4), and although a paucity of the ensemble-mean time series—the single rather than remote. Consider first that in wet
observations prevents an unambiguous dem- time series generated by averaging across the climates, for which soil water is plentiful,
onstration of soil moisture impacts on precip- 16 ensemble members at each time interval, evaporation is controlled not by soil moisture
itation (5), such impacts are often seen in chosen here to be 6 days. We are interested, but by net radiative energy. This is illustrated
atmospheric general circulation model of course, in precipitation; to reduce noise, in Fig. 2, which shows how the ⍀ difference
(AGCM) studies (6, 7). Indeed, some AGCM however, we take X to be the natural loga- diagnostic, applied to evaporation rather than
studies suggest that in continental midlati- rithm of the precipitation. Performing statis- precipitation, varies (on average) with soil
tudes during summer, oceanic impacts on tics on the logarithms of precipitation is a moisture. The ⍀ difference—the fraction of
precipitation are small relative to soil mois- common practice in hydrology and meteorol- the evaporation variance explained by soil
ture impacts (8). ogy, because unmodified precipitation distri- moisture variations—is indeed lowest when
This suggests a question: Are there spe- butions tend to be highly skewed (19, 20). soil moisture is high. Because evaporation in
cific locations on the Earth’s surface for A study of the equation shows that outside wet climates is not highly sensitive to soil
which soil moisture anomalies have a sub- of sampling error, ⍀ should vary from 0 to 1, moisture variations, precipitation should not
stantial impact on precipitation? The identi- with higher values implying a higher impact be sensitive to them, either.
fication of such hot spots would have impor- of the atmosphere’s boundary conditions on Now consider that in dry climates, evap-
tant implications for the design of seasonal precipitation. To isolate soil moisture’s im- oration rates are sensitive to soil moisture
prediction systems and for the associated de- pact on precipitation from that of all other but are also, of course, generally small, as
velopment of ground-based and satellite- forcings, such as time-varying ocean temper- demonstrated for the models by the dashed
based strategies for monitoring soil moisture, atures and the seasonal variation of solar curve in Fig. 2. Intuitively, small evapora-
if such impacts were found to be local. In a radiation, we compute the difference in the ⍀ tion rates should have a limited ability to
broader sense, such identification is critical values between the two ensembles. In simple affect precipitation. The atmosphere in dry
for understanding Earth’s climate system and terms, this ⍀ difference approximates the regions is, in any case, predisposed to limit
the limits of predictability therein. fraction of the precipitation variance ex- precipitation. Only in the transition zones
Although AGCM studies (9–12) and even plained by variations in soil moisture alone. between wet and dry climates, where the
numerical weather prediction model studies Figure 1 shows the global map of the ⍀ atmosphere is amenable to precipitation
(13) have addressed this question, published difference averaged across all of the partici- generation [in particular, where boundary-
results are based on different experimental pating models in GLACE. This multimodel layer moisture can trigger moist convection
designs and reflect distinctive features of dif- estimation of land atmosphere coupling (22)] and where evaporation is suitably
ferent model parameterizations. The coupling strength reveals several distinct hot spots. high but still sensitive to soil moisture, can
question, however, was recently addressed en
masse by a dozen AGCM groups (14), all
performing the same highly controlled nu-
merical experiment. The experiments were
coordinated by GLACE, the Global Land-
Atmosphere Coupling Experiment (15). Each
model contributing to GLACE generated sev-
eral ensembles of boreal summer (June
through August) simulations designed to
quantify that model’s land-atmosphere cou-
pling strength (16) for that season. By com-
bining the results across these models, we
eliminate much of the undesired individual
model dependence. We obtain, in effect, a
unique result: a multimodel average depiction
of the global distribution of land-atmosphere
coupling strength. Given the limitations of
the observational data, both now and in the
foreseeable future, such a multimodel esti-
mate of coupling strength distribution is ar-
guably the best estimate attainable.
Each GLACE participant performed an
ensemble of 16 simulations in which soil
moisture varied between the simulations, and
another ensemble in which the geographical-
Fig. 1. The land-atmosphere coupling strength diagnostic for boreal summer (the ⍀ difference,
ly varying time series of subsurface soil dimensionless, describing the impact of soil moisture on precipitation), averaged across the 12
moisture was forced to be the same across the models participating in GLACE. (Insets) Areally averaged coupling strengths for the 12 individual
16 simulations (17). Coupling strength—the models over the outlined, representative hotspot regions. No signal appears in southern South
degree to which all prescribed boundary con- America or at the southern tip of Africa.

www.sciencemag.org SCIENCE VOL 305 20 AUGUST 2004 1139


REPORTS
we expect soil moisture to influence pre- where many independent models agree that from model to model, because each time series had
cipitation. The major hot spots shown lie the land-atmosphere coupling is important. to be fully consistent with the individual model
using it. The prescribed moistures for a given mod-
mainly in such transition zones (23). The plotted hot spots indicate where a el came, in fact, from one of the model’s simula-
The insets in the map (Fig. 1) show that global initialization of soil moisture may en- tions in the first, “variable soil moisture” ensemble.
not all of the GLACE models place hot hance precipitation prediction skill during In GLACE, subsurface moisture refers to a soil
moisture prognostic variable having an assigned
spots in the regions indicated. In North Northern Hemisphere summer (25, 26). Un- effective depth of more than 5 cm from the sur-
America, for example, only half of the der the assumption that the soil moisture face. Soil moistures corresponding to shallower
models show a statistically significant (24 ) impacts are predominantly local, the hot depths are not reset in the experiment. For details,
see the experiment plan posted on the GLACE Web
coupling strength in the outlined region. spots indicate where the routine monitoring site: http://glace.gsfc.nasa.gov/.
The 12 models agree slightly more in the of soil moisture, with both ground-based and 18. R. D. Koster et al., J. Hydrometeorol. 3, 363 (2002).
Sahelian and Indian hotspot regions; nev- space-based systems, will yield the greatest 19. G. Drufuca, I. I. Zawadzki, J. Appl. Meteorol. 14, 1419
(1975).
ertheless, throughout the world, there exists return in boreal summer seasonal forecasting. 20. B. Kedem, L. S. Chiu, G. R. North, J. Geophys. Res. 95,
extensive intermodel variability in the The hot spots are, in a sense, land-surface 1965 (1990).
strength and positioning of the hot spots, a analogs to the ocean’s “El Niño hot spot” in 21. Indirect (and thus limited in its own right) observa-
tional estimates (28) of the North American hot spot
reflection of ongoing uncertainty in the the eastern tropical Pacific. roughly agree with that shown in the figure.
proper way to represent the physical pro- 22. Y. C. Sud, W. C. Chao, G. K. Walker, J. Arid Environ. 25,
cesses defining land-atmosphere coupling References and Notes 5 (1993).
1. J. M. Wallace et al., J. Geophys. Res. 103, 14241 23. Neither equatorial Africa nor the northernmost
strength. Indeed, some of the models show- (1998). reaches of Canada are traditionally considered tran-
ing a small coupling strength in the insets 2. B. P. Kirtman, P. S. Schopf, J. Clim. 11, 2804 (1998). sition zones between wet and arid climates, and the
also show a low coupling strength every- 3. E. M. Rasmusson, T. H. Carpenter, Mon. Weather Rev. appearance of hot spots in these regions is not so
110, 354 (1982). easily explained. On average, the models do show a
where else on the planet. The intermodel 4. Y. Vinnikov et al., J. Geophys. Res. 101, 7163 (1996). pronounced sensitivity of evaporation to soil mois-
variability highlights the importance of the 5. Historical soil moisture measurements are mostly ture in equatorial Africa, belying its intuitive status as
averaging process leading to Fig. 1. The confined to Asia (27). Even if global soil moisture an atmosphere-controlled evaporation regime.
insets support the idea, stated above, that fields did exist, using observations to establish that 24. For a single model at a single grid cell, an ⍀ differ-
soil moisture affects precipitation is difficult because ence of 0.06 is significant at the 95% confidence
any single-model analysis of coupling the other direction of causality is much stronger— level. If the grid cells within a region are completely
strength will provide model-specific re- precipitation has a first-order impact on soil mois- independent, then a regional (averaged over, say, 10
sults. The patterns revealed by the averag- ture. grid cells) ⍀ difference of 0.002 is significant at the
6. J. Shukla, Y. Mintz, Science 215, 1498 (1982). 95% confidence level. The actual 95% confidence
ing process are valuable because they show 7. P. A. Dirmeyer, J. Clim. 13, 2900 (2000). value for the bars in the histograms lies somewhere
8. R. D. Koster, M. J. Suarez, M. Heiser, J. Hydrometeorol. between these two values, because although multiple
1, 26 (2000). grid cells contribute to the regional average, the grid
9. H. Douville, F. Chauvin, Clim. Dyn. 16, 719 (2000). cells are not fully independent. A single exact value
10. P. A. Dirmeyer, J. Hydrometeorol. 4, 329 (2001). cannot be computed, because each AGCM uses its
11. R. D. Koster, M. J. Suarez, J. Hydrometeorol. 4, 408 own horizontal grid resolution and simulates unique
(2003). spatial correlation structures.
12. C. A. Schlosser, P. C. D. Milly, J. Hydrometeorol. 3, 483 25. This study has focused on soil moisture effects
(2002). alone. Vegetation properties and processes also
13. C. M. Beljaars, P. Viterbo, M. J. Miller, A. K. Betts, Mon. have substantial impacts on climate in a number of
Weather Rev. 124, 362 (1996). regions. For example, Charney et al. (29) describe
14. The participating AGCMs are from the following the importance of surface albedo on North Amer-
groups. ( The order presented here is alphabetical ican climate; Dickinson and Henderson-Sellers (30)
and does not match the order of the histogram show the impact of deforestation on Amazonian
bars in Fig. 1.) (i) Bureau of Meteorology Research climate; and Xue et al. (31) demonstrate the im-
Centre (BMRC), Australia; (ii) The Canadian Center portance of vegetation processes on east Asian
for Climate Modeling and Analysis (CCCma), Can- climate. This issue, like the soil moisture issue, is a
ada; (iii) Center for Climate System Research subject of continuing investigation.
(CCSR), University of Tokyo, and National Institute 26. The relative importance of sea surface temperature
for Environmental Studies (NIES), Japan; (iv) Cen- (SST) forcing in the indicated hot spots cannot be
ter for Ocean-Land-Atmosphere Studies (COLA), determined in this experiment, for two reasons. (i)
United States; (v) Commonwealth Scientific and The SST signal in either of the two ensembles cannot
Industrial Research Organization (CSIRO), Austra- be separated from the strong seasonality signal as-
lia; (vi) NASA/Goddard Space Flight Center Labo- sociated with the Sun’s transit across the sky over the
ratory for Atmospheres, Climate and Radiation 3-month simulation period. (ii) Only a single year of
Branch, United States (GEOS); (vii) Geophysical SSTs is prescribed, so the effect of interannually
Fluid Dynamics Laboratory (GFDL), United States; varying SSTs is not captured. As noted in the text,
(viii) Hadley Center (HadAM3), UK; (ix) National some studies (8) show a strong SST impact in the
Center for Atmospheric Research (NCAR), United tropics and subtropics (encompassing the indicated
Fig. 2. Average relationship between soil wet- States; (x) National Center for Environmental Pre- hot spots in Africa and southern Asia) and a relatively
ness (the degree of saturation in the soil) and diction (NCEP), United States; (xi) NASA Seasonal- weak impact in midlatitudes (encompassing the
two separate aspects of the land-surface ener- to-Interannual Prediction Project [now part of the North American hot spot).
gy budget: the ⍀ difference for evaporation Global Modeling and Assimilation Office (GMAO)], 27. A. Robock et al., Bull. Am. Meteorol. Soc. 81, 1281
(solid curve, in dimensionless units) and the United States; and (xiii) University of California, (2000).
Los Angeles (UCLA). 28. R. D. Koster, M. J. Suarez, R. W. Higgins, H. M. Van den
average evaporation rate (dashed curve, in cm/ 15. GLACE is a joint project of the Global Energy and Dool, Geophys. Res. Lett. 30, 1241, 10.1029/
day). Both aspects should have suitably high Water Cycle Experiment (GEWEX ) Global Land At- 2002GL016571 (2003).
values to allow soil moisture anomalies to be mosphere System Study (GLASS) and the Climate 29. J. Charney, W. J. Quirk, S. H. Chow, J. Kornfield, J.
translated into precipitation anomalies; the Variability Experiment (CLIVAR) Working Group on Atmos. Sci. 34, 1366 (1977).
plot shows that this mostly occurs for interme- Seasonal-to-Interannual Prediction (WGSIP), all un- 30. R. E. Dickinson, A. Henderson-Sellers, Q. J. R. Meteo-
diate values of soil wetness, i.e., in the transi- der the aegis of the World Climate Research Pro- rol. Soc. 114, 439 (1988).
tion zones between wet and dry climates. The gramme (WCRP). 31. Y. K. Xue et al., J. Geophys. Res. 109, D03105,
curves are derived by averaging the soil wet- 16. Coupling strength in this report refers to the general 10.1029/2003JD003556 (2004).
ability of land surface moisture anomalies— either 32. We thank the listed institutions for the computation-
ness, ⍀ difference, and evaporation fields local or remote—to affect precipitation in a given al support needed to perform the simulations. We
across the 12 models, constructing scatter plots region. Inferences regarding soil moisture measure- also thank M. Kistler for help with the GLACE project
for the two relationships with data from non- ment in the indicated hot spots require an assump- Web page and T. Bell for statistical advice.
ice land points, and then binning the data ac- tion of local influence.
cording to soil wetness value. 17. The prescribed soil moistures necessarily differed 12 May 2004; accepted 7 July 2004

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