Person:

Jacob, Daniel

Space-borne formaldehyde (HCHO) column measurements from the Ozone Monitoring Instrument (OMI), with 13 × 24 km2 nadir footprint and daily global coverage, provide new constraints on the spatial distribution of biogenic isoprene emission from North America. OMI HCHO columns for June-August 2006 are consistent with measurements from the earlier GOME satellite sensor (1996–2001) but OMI is 2–14% lower. The spatial distribution of OMI HCHO columns follows that of isoprene emission; anthropogenic hydrocarbon emissions are undetectable except in Houston. We develop updated relationships between HCHO columns and isoprene emission from a chemical transport model (GEOS-Chem), and use these to infer top-down constraints on isoprene emissions from the OMI data. We compare the OMI-derived emissions to a state-of-science bottom-up isoprene emission inventory (MEGAN) driven by two land cover databases, and use the results to optimize the MEGAN emission factors (EFs) for broadleaf trees (the main isoprene source). The OMI-derived isoprene emissions in North America (June–August 2006) with 1° × 1° resolution are spatially consistent with MEGAN (R2 = 0.48–0.68) but are lower (by 4–25% on average). MEGAN overestimates emissions in the Ozarks and the Upper South. A better fit to OMI (R2 = 0.73) is obtained in MEGAN by using a uniform isoprene EF from broadleaf trees rather than variable EFs. Thus MEGAN may overestimate emissions in areas where it specifies particularly high EFs. Within-canopy isoprene oxidation may also lead to significant differences between the effective isoprene emission to the atmosphere seen by OMI and the actual isoprene emission determined by MEGAN.

Concurrent (August 2006) measurements of tropospheric NO2 columns from OMI aboard Aura (1330 local overpass time) and SCIAMACHY aboard Envisat (1000 local overpass time) offer an opportunity to examine the consistency between the two instruments under tropospheric background conditions and the effect of different observing times. For scenes with tropospheric NO2 columns <5.0 × 1015 molecules cm−2, SCIAMACHY and OMI agree within 1.0–2.0 × 1015 molecules cm−2, consistent with the detection limits of both instruments. We find evidence for a low bias of 0.2 × 1015 molecules cm−2 in OMI observations over remote oceans. Over the fossil fuel source regions at northern midlatitudes, we find that SCIAMACHY observes up to 40% higher NO2 at 1000 local time (LT) than OMI at 1330 LT. Over biomass burning regions in the tropics, SCIAMACHY observes up to 40% lower NO2 columns than OMI. These differences are present in the spectral fitting of the data (slant column) and are augmented in the fossil fuel regions and dampened in the tropical biomass burning regions by the expected increase in air mass factor as the mixing depth rises from 1000 to 1330 LT. Using a global 3-D chemical transport model (GEOS-Chem), we show that the 1000–1330 LT decrease in tropospheric NO2 column over fossil fuel source regions can be explained by photochemical loss, dampened by the diurnal cycle of anthropogenic emissions that has a broad daytime maximum. The observed 1000–1330 LT NO2 column increase over tropical biomass burning regions points to a sharp midday peak in emissions and is consistent with a diurnal cycle of emissions derived from geostationary satellite fire counts.

Understanding the biogeochemical cycling of mercury is critical for explaining the presence of mercury in remote regions of the world, such as the Arctic and the Himalayas, as well as local concentrations. While we have good knowledge of present-day fluxes of mercury to the atmosphere, we have little knowledge of what emission levels were like in the past. Here we develop a trend of anthropogenic emissions of mercury to the atmosphere from 1850 to 2008— for which relatively complete data are available—and supplement that trend with an estimate of anthropogenic emissions prior to 1850. Global mercury emissions peaked in 1890 at 2600 Mg yr(^{ -1}), fell to 700 800 Mg yr( ^{-1}) in the interwar years, then rose steadily after 1950 to present-day levels of 2000 Mg yr(^- 1). Our estimate for total mercury emissions from human activities over all time is 350 Gg, of which 39% was emitted before 1850 and 61% after 1850. Using an eight-compartment global box-model of mercury biogeochemical cycling, we show that these emission trends successfully reproduce present-day atmospheric enrichment in mercury.

Formation of SOA from the aromatic species toluene, xylene, and, for the first time, benzene, is added to a global chemical transport model. A simple mechanism is presented that accounts for competition between low and high-yield pathways of SOA formation, wherein secondary gas-phase products react further with either nitric oxide (NO) or hydroperoxy radical ((HO_2)) to yield semi- or non-volatile products, respectively. Aromatic species yield more SOA when they react with OH in regions where the ([NO]/[HO_2]) ratios are lower. The SOA yield thus depends upon the distribution of aromatic emissions, with biomass burning emissions being in areas with lower ([NO]/[HO_2]) ratios, and the reactivity of the aromatic with respect to OH, as a lower initial reactivity allows transport away from industrial source regions, where ([NO]/[HO_2]) ratios are higher, to more remote regions, where this ratio is lower and, hence, the ultimate yield of SOA is higher. As a result, benzene is estimated to be the most important aromatic species with regards to global formation of SOA, with a total production nearly equal that of toluene and xylene combined. Global production of SOA from aromatic sources via the mechanisms identified here is estimated at 3.5 Tg/yr, resulting in a global burden of 0.08 Tg, twice as large as previous estimates. The contribution of these largely anthropogenic sources to global SOA is still small relative to biogenic sources, which are estimated to comprise 90% of the global SOA burden, about half of which comes from isoprene. Uncertainty in these estimates owing to factors ranging from the atmospheric relevance of chamber conditions to model deficiencies result in an estimated range of SOA production from aromatics of 2–12 Tg/yr. Though this uncertainty range affords a significant anthropogenic contribution to global SOA, it is evident from comparisons to recent observations that additional pathways for production of anthropogenic SOA still exist beyond those accounted for here. Nevertheless, owing to differences in spatial distributions of sources and seasons of peak production, regions exist in which aromatic SOA produced via the mechanisms identified here are predicted to contribute substantially to, and even dominate, the local SOA concentrations, such as outflow regions from North America and South East Asia during the wintertime, though total modeled SOA concentrations there are small ((\sim0.1 \mu g/m^3)).

We investigate the climate response to changing US anthropogenic aerosol sources over the 1950–2050 period by using the NASA GISS general circulation model (GCM) and comparing to observed US temperature trends. Time-dependent aerosol distributions are generated from the GEOS-Chem chemical transport model applied to historical emission inventories and future projections. Radiative forcing from US anthropogenic aerosols peaked in 1970–1990 and has strongly declined since due to air quality regulations. We find that the regional radiative forcing from US anthropogenic aerosols elicits a strong regional climate response, cooling the central and eastern US by 0.5–1.0 °C on average during 1970–1990, with the strongest effects on maximum daytime temperatures in summer and autumn. Aerosol cooling reflects comparable contributions from direct and indirect (cloud-mediated) radiative effects. Absorbing aerosol (mainly black carbon) has negligible warming effect. Aerosol cooling reduces surface evaporation and thus decreases precipitation along the US east coast, but also increases the southerly flow of moisture from the Gulf of Mexico resulting in increased cloud cover and precipitation in the central US. Observations over the eastern US show a lack of warming in 1960–1980 followed by very rapid warming since, which we reproduce in the GCM and attribute to trends in US anthropogenic aerosol sources. Present US aerosol concentrations are sufficiently low that future air quality improvements are projected to cause little further warming in the US (0.1 °C over 2010–2050). We find that most of the warming from aerosol source controls in the US has already been realized over the 1980–2010 period.

We calculate decadal aerosol direct and indirect (warm cloud) radiative forcings from US anthropogenic sources over the 1950–2050 period. Past and future aerosol distributions are constructed using GEOS-Chem and historical emission inventories and future projections from the IPCC A1B scenario. Aerosol simulations are evaluated with observed spatial distributions and 1980–2010 trends of aerosol concentrations and wet deposition in the contiguous US. Direct and indirect radiative forcing is calculated using the GISS general circulation model and monthly mean aerosol distributions from GEOS-Chem. The radiative forcing from US anthropogenic aerosols is strongly localized over the eastern US. We find that its magnitude peaked in 1970–1990, with values over the eastern US (east of 100° W) of −2.0 W m−2 for direct forcing including contributions from sulfate (−2.0 W m−2), nitrate (−0.2 W m−2), organic carbon (−0.2 W m−2), and black carbon (+0.4 W m−2). The uncertainties in radiative forcing due to aerosol radiative properties are estimated to be about 50%. The aerosol indirect effect is estimated to be of comparable magnitude to the direct forcing. We find that the magnitude of the forcing declined sharply from 1990 to 2010 (by 0.8 W m−2 direct and 1.0 W m−2 indirect), mainly reflecting decreases in SO2 emissions, and project that it will continue declining post-2010 but at a much slower rate since US SO2 emissions have already declined by almost 60% from their peak. This suggests that much of the warming effect of reducing US anthropogenic aerosol sources has already been realized. The small positive radiative forcing from US BC emissions (+0.3 W m−2 over the eastern US in 2010; 5% of the global forcing from anthropogenic BC emissions worldwide) suggests that a US emission control strategy focused on BC would have only limited climate benefit.

Methylmercury is a potent neurotoxin that accumulates in aquatic food webs. Human activities, including industry and mining, have increased inorganic mercury inputs to terrestrial and aquatic ecosystems. Methylation of this mercury generates methylmercury, and is thus a public health concern. Marine methylmercury is a particular concern in the Arctic, where indigenous peoples rely heavily on marine-based diets. In the summer, atmospheric inorganic mercury concentrations peak in the Arctic, whereas they reach a minimum in the northern mid-latitudes. Here, we use a global three-dimensional ocean–atmosphere model to examine the cause of this Arctic summertime maximum. According to our simulations, circumpolar rivers deliver large quantities of mercury to the Arctic Ocean during summer; the subsequent evasion of this riverine mercury to the atmosphere can explain the summertime peak in atmospheric mercury levels. We infer that rivers are the dominant source of mercury to the Arctic Ocean on an annual basis. Our simulations suggest that Arctic Ocean mercury concentrations could be highly sensitive to climate-induced changes in river flow, and to increases in the mobility of mercury in soils, for example as a result of permafrost thaw and forest fires.

We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by <1–8 nmol mol−1 (6.5% globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4%. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40% higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

We applied a multiple linear regression model to understand the relationships of PM2.5 with meteorological variables in the contiguous US and from there to infer the sensitivity of PM2.5 to climate change. We used 2004–2008 PM2.5 observations from ~1000 sites (~200 sites for PM2.5 components) and compared to results from the GEOS-Chem chemical transport model (CTM). All data were deseasonalized to focus on synoptic-scale correlations. We find strong positive correlations of PM2.5 components with temperature in most of the US, except for nitrate in the Southeast where the correlation is negative. Relative humidity (RH) is generally positively correlated with sulfate and nitrate but negatively correlated with organic carbon. GEOS-Chem results indicate that most of the correlations of PM2.5 with temperature and RH do not arise from direct dependence but from covariation with synoptic transport. We applied principal component analysis and regression to identify the dominant meteorological modes controlling PM2.5 variability, and show that 20–40% of the observed PM2.5 day-to-day variability can be explained by a single dominant meteorological mode: cold frontal passages in the eastern US and maritime inflow in the West. These and other synoptic transport modes drive most of the overall correlations of PM2.5 with temperature and RH except in the Southeast. We show that interannual variability of PM2.5 in the US Midwest is strongly correlated with cyclone frequency as diagnosed from a spectral-autoregressive analysis of the dominant meteorological mode. An ensemble of five realizations of 1996–2050 climate change with the GISS general circulation model (GCM) using the same climate forcings shows inconsistent trends in cyclone frequency over the Midwest (including in sign), with a likely decrease in cyclone frequency implying an increase in PM2.5. Our results demonstrate the need for multiple GCM realizations (because of climate chaos) when diagnosing the effect of climate change on PM2.5, and suggest that analysis of meteorological modes of variability provides a computationally more affordable approach for this purpose than coupled GCM-CTM studies.

[1] We analyze 1977–2010 trends in atmospheric mercury (Hg) from 21 ship cruises over the North Atlantic (NA) and 15 over the South Atlantic (SA). We find a steep 1990–2009 decline of −0.046 ± 0.010 ng m−3 a−1 (−2.5% a−1) over the NA (steeper than at Northern Hemispheric land sites) but no significant decline over the SA. Surface water Hg0 measurements in the NA show a decline of −5.7% a−1since 1999, and limited subsurface ocean data show an ∼80% decline from 1980 to present. We use a coupled global atmosphere-ocean model to show that the decline in NA atmospheric concentrations can be explained by decreasing oceanic evasion from the NA driven by declining subsurface water Hg concentrations. We speculate that this large historical decline of Hg in the NA Ocean could have been caused by decreasing Hg inputs from rivers and wastewater and by changes in the oxidant chemistry of the atmospheric marine boundary layer.