Long-Term and Seasonal Variations in CO2: Linkages to Catchment Alkalinity Generation

As atmospheric emissions of S have declined in the Northern Hemisphere, there has been an expectation of increased pH and alkalinity in streams believed to have been acidified by excess S and N. Many streams and lakes have not recovered. Evidence from East Bear Brook in Maine, USA and modelling with the groundwater acid-base model MAGIC (Cosby et al. 1985a,b) indicate that seasonal and yearly variations in soil PCO2 are adequate to enhance or even reverse acid-base (alkalinity) changes anticipated from modest decreases of SO4 in surface waters. Alkalinity is generated in the soil by exchange of H+ from dissociation of H2CO3, which in turn is derived from the dissolving of soil CO2. The variation in soil PCO2 produces an alkalinity variation of up to 15 mu eq L-1 in stream water. Detecting and relating increases in alkalinity to decreases in stream SO4 are significantly more difficult in the short term because of this effect. For example, modelled alkalinity recovery at Bear Brook due to a decline of 20 mu eq SO4 L-1 in soil solution is compensated by a decline from 0.4 to 0.2% for soil air PCO2. This compensation ability decays over time as base saturation declines. Variable PCO2 has less effect in more acidic soils. Short-term decreases of PCO2 below the long-term average value produce short-term decreases in alkalinity, whereas short-term increases in PCO2 produce shortterm alkalization. Trend analysis for detecting recovery of streams and lakes from acidification after reduced atmospheric emissions will require a longer monitoring period for statistical significance than previously appreciated.

Particulate Backscattering Ratio at Leo 15 and Its Use to Study Particle Composition and Distribution

Particulate scattering and backscattering are two quantities that have traditionally been used to quantify in situ particulate concentration. The ratio of the backscattering by particles to total scattering by particles (the particulate backscattering ratio) is weakly dependent on concentration and therefore provides us with information on the characteristics of the particulate material, such as the index of refraction. The index of refraction is an indicator of the bulk particulate composition, as inorganic minerals have high indices of refraction relative to oceanic organic particles such as phytoplankton and detrital material that typically have a high water content. We use measurements collected near the Rutgers University Long-term Ecosystem Observatory in 15 m of water in the Mid-Atlantic Bight to examine application of the backscattering ratio. Using four different instruments, the HOBILabs Hydroscat-6, the WETLabs ac-9 and EcoVSF, and a prototype VSF meter, three estimates of the ratio of the particulate backscattering ratio were obtained and found to compare well. This is remarkable because these are new instruments with large differences in design and calibration. The backscattering ratio is used to map different types of particles in the nearshore region, suggesting that it may act as a tracer of water movement. We find a significant relationship between the backscattering ratio and the ratio of chlorophyll to beam attenuation. This implies that these more traditional measurements may be used to identify when phytoplankton or inorganic particles dominate. In addition, it provides an independent confirmation of the link between the backscattering ratio and the bulk composition of particles.