Coastal Ocean Last Glacial Maximum to 2100 CO2-Carbonic Acid-Carbonate System: A Modeling Approach

Using coupled terrestrial and coastal zone models, we investigated the impacts of deglaciation and anthropogenic inputs on the CO₂–H₂O–CaCO₃ system in global coastal ocean waters from the Last Glacial Maximum (LGM: 18,000 year BP) to the year 2100. With rising sea level and atmospheric CO₂, the carbonate system of coastal ocean water changed significantly. We find that 6 × 10¹² metric tons of carbon were emitted from the coastal ocean, growing due to the sea level rise, from the LGM to late preindustrial time (1700 AD) because of net heterotrophy and calcification processes. This carbon came to reside in the atmosphere and in the growing vegetation on land and in uptake of atmospheric CO₂ through the weathering of rocks on land. It appears that carbonate accumulation, mainly, but not exclusively, in coral reefs from the LGM to late preindustrial time could account for about 24 ppmv of the 100 ppmv rise in atmospheric CO₂, lending some support to the “coral reef hypothesis”. In addition, the global coastal ocean is now, or soon will be, a sink of atmospheric CO₂. The temperature rise of 4–5°C since the LGM led to increased weathering rates of inorganic and organic materials on land and enhanced riverine fluxes of total C, N, and P to the coastal ocean of 68%, 108%, and 97%, respectively, from the LGM to late preindustrial time. During the Anthropocene, these trends have been exacerbated owing to rising atmospheric CO₂, due to fossil fuel combustion and land-use practices, other human activities, and rising global temperatures. River fluxes of total reactive C, N, and P are projected to increase from late preindustrial time to the year 2100 by 150%, 380%, and 257%, respectively, modifying significantly the behavior of these element cycles in the coastal ocean, particularly in proximal environments. Despite the fact that the global shoal water carbonate mass has grown extensively since the LGM, the pH_T (pH values on the total proton scale) of global coastal waters has decreased from ~8.35 to ~8.18 and the carbonate ion concentration declined by ~19% from the LGM to late preindustrial time. The latter represents a rate of decline of about 0.028 μmol CO₃ ^2? per decade. In comparison, the decrease in coastal water pH_T from the year 1900 to 2000 was about 8.18–8.08 and is projected to decrease further from about 8.08 to 7.85 between 2000 and 2100, according to the IS92a business-as-usual scenario of CO₂ emissions. Over these 200 years, the carbonate ion concentration will fall by ~120 μmol kg^?1 or 6 μmol kg^?1 per decade. This decadal rate of decline of the carbonate ion concentration in the Anthropocene is 214 times the average rate of decline for the entire Holocene. Hence, when viewed against the millennial to several millennial timescale of geologic change in the coastal ocean marine carbon system, one can easily appreciate why ocean acidification is the “other CO₂ problem”.     

Tentative kinetic model for dolomite precipitation rate and its application to dolomite distribution

The dolomite problem has a long history and remains one of the most intensely studied and debated topics in geology. Major amounts of dolomite are not directly forming today from seawater. This observation has led many investigators to develop geochemical/hydrologic models for dolomite formation in diagenetic environments. A fundamental limitation of the current models for the growth of sedimentary dolomite is the dearth of kinetic information for this phase, in contrast to that available for calcite and aragonite.We present a simple kinetic model describing dolomite growth as a function of supersaturation using data from published high temperature synthesis experiments and our own experimental results. This model is similar in form to empirical models used to describe precipitation and dissolution rates of other carbonate minerals. Despite the considerable uncertainties and assumptions implicit in this approach, the model satisfies a basic expectation of classical precipitation theory, i.e., that the distance from equilibrium is a basic driving force for reaction rate. The calculated reaction order is high (~ 3), and the combined effect of high order and large activation energy produces a very strong dependence of the rate on temperature and the degree of supersaturation of aqueous solutions with respect to this phase.Using the calculated parameters, we applied the model to well-documented case studies of sabkha dolomite at Abu Dhabi (Persian Gulf), and organogenic dolomite from the Gulf of California. Growth rates calculated from the model agree with independent estimates of the age of these dolomites to well within an order of magnitude. A comparison of precipitation rates in seawater also shows the rate of dolomite precipitation to converge strongly with that of calcite with increasing temperature. If correct, this result implies that dolomite may respond to relatively modest warming of surface environments by substantial increases in accumulation rate, and suggests that the distribution of sedimentary dolomite in the rock record may be to some extent a temperature signal.     

An Evaluation of Interpolation Methodologies for Generating Three-Dimensional Hydraulic Property Distributions from Measured Data

The process of attempting to model ground-water systems requires a good understanding of the spatial variation of aquifer hydraulic properties. The capabilities of the more recent innovative flowmeters such as the electromagnetic and heat pulse flowmeters provide the sensitivity to measure ambient flows and pump-induced flows. These flowmeters provide the measurements of pump-induced vertical flows which are analyzed to obtain vertical variations in horizontal hydraulic conductivity, K(z). With discrete areal K-values, K(x, y), and vertical profiles of K, provided by multiwell testing, the essential elements are present to produce a three-dimensional hydraulic conductivity field. The advent of these new flow measuring devices has contributed much to the motivation behind this paper. This paper presents the results of applying deterministic and stochastic methodology to the three-dimensional interpolation of hydraulic properties, specifically, hydraulic conductivity, K. Three of the approaches applied in this paper are deterministic in nature, inverse-distance weighting, inverse-distance-squared weighting, and ordinary kriging, while the fourth is a stochastic approach based on self-affine fractals. All of the methods are applied to measured data collected from 14 wells at a site in the United States near Mobile, Alabama. The three-dimensional K-distributions generated by each of the methods are used as inputs to an advective based transport model with the resulting model output compared to a two-well tracer study run previously at the same site.     

A molybdenum oxide annular denuder system for gas phase ambient ammonia measurements

An automated molybdenum oxide annular denuder system (MOADS) has been developed for gas phase ambient ammonia measurements. This system combines high sensitivity (detection limit <50 pptv) with continuous sampling, moderate collection times (30 min) and automated operation. The present denuder design confers two important advantages over the tungsten oxide coated quartz denuder tubes used previously for nitric acid and ammonia measurements. First, the present denuders use oxidized metal substrates and are easier to fabricate and more durable than denuders made from metal oxide coated glass or quartz tubes. Second, molybdenum (VI) oxide surfaces are used which oxidize a reproducible fraction of the adsorbed NH₃ directly to NO upon desorption eliminating the need for a secondary catalytic converter. Laboratory tests of the collection/recovery characteristics of annular denuders made from both the (IV) and (VI) oxides of tungsten and molybdenum are described and preliminary results from field tests are presented.     

Interpretation of metal concentrations in estuarine sediments of Florida using aluminum as a reference element

Metal contamination of estuarine sediments is an increasing problem in Florida and elsewhere as urbanization extends into previously undeveloped areas. Effective estuarine management practices require scientifically valid tools to assess the extent of estuarine contamination. Interpretation of anthropogenic metal contributions has been hampered by the fact that natural metal concentrations in sediments vary by orders of magnitude in different sediments. Normalization of metal concentrations to a reference element, aluminum, appears to be a promising method for comparing estuarine sediment metal concentrations on a regional basis. In this paper we describe an interpretive method based on the relationship between sediment metals and aluminum derived from statewide data on natural estuarine sediments in Florida. We show how the method can be used to interpret metal concentrations with an example using data from the Miami River and Biscayne Bay.