Vertical column amounts of nitrogen dioxide, C(NO2), are derived from ground‐based direct solar irradiance measurements using two new and independently developed spectrometer systems, Pandora (Goddard Space Flight Center) and MFDOAS (Washington State University). We discuss the advantages of C(NO2) retrievals based on Direct Sun ‐ Differential Optical Absorption Spectroscopy (DS‐DOAS). The C(NO2) data are presented from field campaigns using Pandora at Aristotle University (AUTH), Thessaloniki, Greece; a second field campaign involving both new instruments at Goddard Space Flight Center (GSFC), Greenbelt, Maryland; a Pandora time series from December 2006 to October 2008 at GSFC; and a MFDOAS time series for spring 2008 at Pacific Northwest National Laboratory (PNNL), Richland, Washington. Pandora and MFDOAS were compared at GFSC and found to closely agree, with both instruments having a clear‐sky precision of 0.01 DU (1 DU = 2.67 × 1016 molecules/cm2) and a nominal accuracy of 0.1 DU. The high precision is obtained from careful laboratory characterization of the spectrometers (temperature sensitivity, slit function, pixel to pixel radiometric calibration, and wavelength calibration), and from sufficient measurement averaging to reduce instrument noise. The accuracy achieved depends on laboratory‐measured absorption cross sections and on spectrometer laboratory and field calibration techniques used at each measurement site. The 0.01 DU precision is sufficient to track minute‐by‐minute changes in C(NO2) throughout each day with typical daytime values ranging from 0.2 to 2 DU. The MFDOAS instrument has better noise characteristics for a single measurement, which permits MFDOAS to operate at higher time resolution than Pandora for the same precision. Because Pandora and MFDOAS direct‐sun measurements can be made in the presence of light to moderate clouds, but with reduced precision (∼0.2 DU for moderate cloud cover), a nearly continuous record can be obtained, which is important when matching OMI overpass times for satellite data validation. Comparisons between Pandora and MFDOAS with OMI are discussed for the moderately polluted GSFC site, between Pandora and OMI at the AUTH site, and between MFDOAS and OMI at the PNNL site. Validation of OMI measured C(NO2) is essential for the scientific use of the satellite data for air quality, for atmospheric photolysis and chemistry, and for retrieval of other quantities (e.g., accurate atmospheric correction for satellite estimates of ocean reflectance and bio‐optical properties). Changes in the diurnal variability of C(NO2) with season and day of the week are presented based on the 2‐year time series at GSFC measured by the Pandora instrument.

The role of tidal marshes as a source of dissolved organic carbon (DOC) and colored dissolved organic matter (CDOM) for adjacent estuarine waters was studied in the Rhode River subestuary of the Chesapeake Bay. Water in a tidal creek draining brackish, high-elevation marshes was sampled every hour during several semidiurnal tidal cycles in order to examine the tidal exchange of dissolved organic matter (DOM). Water leaving the marsh during ebbing tide was consistently enriched in DOC compared to water entering the marsh during flooding tide. There was a net DOC export from the marsh to the estuary during seasons of both low and high marsh plant biomass. Optical analysis demonstrated that, in addition to contributing to the carbon budgets, the marsh had a strong influence on the estuary's CDOM dynamics. Marsh-exported CDOM had optical properties that were consistently and markedly different from those of CDOM in the adjacent estuary. Specifically, marsh CDOM had: (1) considerably stronger absorption, (2) larger DOC-specific absorption, (3) lower exponential spectral slope, (4) larger fluorescence signal, (5) lower fluorescence per unit absorbance, and (6) higher fluorescence at wavelengths .400 nm. These optical characteristics are indicative of relatively complex, high-molecular-weight, aromatic-rich DOM, and this was confirmed by results of molecular-weight-distribution analysis. Our findings illustrate the importance of tidal marshes as sources of optically and chemically distinctive dissolved organic compounds, and their influence on CDOM dynamics, DOC budgets, and, thus, photochemical and biogeochemical processes, in adjacent estuarine ecosystems.

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