Prediction of the abiotic degradability of organic compounds in the troposphere

A statistically relevant correlation between the reaction rate coefficient, k _OH, for the OH radical reaction with 161 organic compounds in the gas phase at 300 K, and the corresponding vertical ionisation energies E _i,v, reveals two classes of compounds: aromatics where –log(k _OH/cm³s^-1)3/2E _i,v(eV)–2 and aliphatics where –log(k _OH/cm³s^-1)4/5E _i,v(eV)+3. The prediction of the rate coefficient, k _OH, for the reaction of OH with organic molecules from the above equations has a probability of about 90%. Assuming a global diurnal mean of the OH radical concentration of 5×10⁵ cm³, the upper limit of the tropospheric half-life of organic compounds and their persistence can be estimated.     

Predicting summer hypoxia in the northern Gulf of Mexico: riverine N, P, and Si loading

We conducted a statistical analysis to discern the relative strengths of the loading of various forms of nitrogen, phosphorus, dissolved silicate and their molar ratios on the variance in the size of the summertime low oxygen zone found off the Mississippi River, northern Gulf of Mexico. A stable statistical model that included Year and riverine nitrate+nitrite loading for the 2 months prior to the measurement of hypoxic zone size described 82% of its variation in size from 1978 to 2004. The usefulness of the term Year is consistent with the documented increase in carbon stored in sediments after the 1970s, which is when the hypoxic zone is predicted to have become a regular feature on the shelf and to have expanded westward. The increased carbon storage is anticipated to cause a sedimentary respiratory demand influencing the size of the zone, and whose temporal influence is cumulative and transcends the annual variations in nitrogen loading. The variable Year is negatively correlated with the TN:TP ratio in a way that suggests N, not P, has become more important as a factor limiting phytoplankton growth in the last 20 years. Nitrogen, in particular nitrate+nitrite, and not phosphorus, dissolved silicate, or their molar ratios, appears to be the major driving factor influencing the size of the hypoxic zone on this shelf. This conclusion is consistent with cross-system analyses that conclude that the TN:TP ratio in the Mississippi River, currently fluctuating around 20:1, is indicative of nitrogen, not phosphorus, limitation of phytoplankton growth. Nutrient management that places stronger emphasis on reducing nitrogen loading as compared to phosphorus loading, is justified.     

A modeling study of the physical processes affecting the development of seasonal hypoxia over the inner Louisiana-Texas shelf: Circulation and stratification

The physical processes affecting the development of seasonal hypoxia over the Louisiana-Texas shelf were examined using a high-resolution, three-dimensional, unstructured-grid, Finite Volume Coastal Ocean Model (FVCOM). The model was forced with the observed freshwater fluxes from the Mississippi and Atchafalaya Rivers, surface winds, heat fluxes, tides and offshore conditions. The simulations were carried out over a six-month period, from April to September 2002, and the model performance was evaluated against several independent series of observations that included tidal gauge data, Acoustic Doppler Current Profiler (ADCP) data, shipboard measurements of temperature and salinity, vertical salinity and sigma-t profiles, and satellite imagery. The model accurately described the offshore circulation mode generated over the Louisiana-Texas shelf by the westerly winds during summer months, as well as the prevalent westward flow along the coast caused by the easterly winds during the rest of the study period. The seasonal cycle of stratification also was well represented by the model. During 2002, the stratification was initiated in early spring and subsequently enhanced by the intensity and phasing of riverine freshwater discharges. Strong stratification persisted throughout the summer and was finally broken down in September by tropical storms. The model simulations also revealed a quasi-permanent anticyclonic gyre in the Louisiana Bight region formed by the rotational transformation of the Mississippi River plume, whose existence during 2002 was supported by the satellite imagery and ADCP current measurements. Model simulations support the conclusion that local wind forcing and buoyancy flux resulting from riverine freshwater discharges were the dominant mechanisms affecting the circulation and stratification over the inner Louisiana-Texas shelf.     

Reducing hypoxia in the Gulf of Mexico: Advice from three models

Summer hypoxia in the bottom waters of the northern Gulf of Mexico has received considerable scientific and policy attention because of potential ecological and economic impacts from this very large zone of low oxygen and because of the implications for management within the massive Mississippi River watershed. An assessment of its causes and consequences concluded that the almost 3-fold increase in nitrogen load to the Gulf is the primary external driver stimulating the increase in hypoxia since the middle of the last century. Results from three very different models are compared to reach the consensus that large-sclae hypoxia likely did not start in the Gulf of Mexico until the mid-1970s and that the 30% nitrogen load reduction called for in an Action Plant to reduce hypoxia, agreed to by a federal, state, and tribal task force, may not be sufficient to reach the plan’s goal. Caution is also raised for setting resource management goals without considering the long-term consequences of climate variability and change.     

Future aquatic nutrient limitations

Nutrient limitation of phytoplankton growth in aquatic systems is moving towards a higher incidence of P and Si limitation as a result of increased nitrogen loading, a N:P fertilizer use of 26:1 (molar basis), population growth, and relatively stable silicate loading. This result will likely alter phytoplankton community composition, and may compromise diatom-->zooplankton-->fish food webs.     

Development of Productivity Models for the Northern Gulf of Mexico Based on Oxygen Concentrations and Stable Isotopes

Oxygen concentrations have been used for decades to estimate primary production (P) and respiration (R) in aquatic ecosystems. Yet, this approach cannot separate the effects of biological and physical processes affecting oxygen dynamics; therefore, it is now often complemented with the analysis of stable oxygen isotopes. Existing algorithms for calculating primary production and P/R have been developed for closed systems and steady-state open systems. None of these formulations are applicable to productive aquatic ecosystems where diurnal changes in oxygen concentrations and isotope values are usually large. Here, we describe a novel P/R model that includes algorithms for air–sea gas exchange and is not constrained by steady-state conditions. Our objective was to test model sensitivity to variations in input parameters for values commonly observed in coastal waters of the northern Gulf of Mexico. The model was highly sensitive to variations in fractionation factor for respiration (ε) but less sensitive to variations in wind speed, oxygen isotope values of source-water, or oxygen flux through the picnocline. This model is easily transferable to other coastal ecosystems, with a caveat that system-specific values for ε are needed to obtain realistic estimates of P/R.     

Nutrient changes in the Mississippi River and system responses on the adjacent continental shelf

The Mississippi River system ranks among the world's top 10 rivers in freshwater and sediment inputs to the coastal ocean. The river contributes 90% of the freshwater loading to the Gulf of Mexico, and terminates amidst one of the United States' most productive fisheries regions and the location of the largest zone of hypoxia, in the western Atlantic Ocean. Significant increases in riverine nutrient concentrations and loadings of nitrate and phosphorus and decreases in silicate have occurred this century, and have accelerated since 1950. Consequently, major alterations have occurred in the probable nutrient limitation and overall stoichiometric nutrient balance in the adjacent continental shelf system. Changes in the nutrient balances and reduction in riverine silica loading to, the continental shelf appear to have led to phytoplankton species shifts offshore and to an increase in primary production. The phytoplankton community response, as indicated by long-term changes in biological uptake of silicate and accumulation of biologically bound silica in sediments, has shown how the system has responded to changes in riverine nutrient loadings. Indeed, the accumulation of biologically bound silica in sediments beneath the Mississippi River plume increased during the past two decades, presumably in response to, increased nitrogen loading. The duration, size, and severity of hypoxia has probably increased as a consequence of the increased primary production. Management alternatives directed at water pollution issues within the Mississippi River watershed may have unintended and contrasting impacts on the coastal waters of the northern Gulf of Mexico.     

Nitrogen and phosphorus transport between Fourleague Bay, LA, and the Gulf of Mexico: the role of winter cold fronts and Atchafalaya River discharge

Nutrient fluxes were measured between Fourleague Bay, a shallow Louisiana estuary, and the Gulf of Mexico every 3 h between February 1 and April 30, 1994 to determine how high velocity winds associated with cold fronts and peak Atchafalaya River discharge influenced transport. Net water fluxes were ebb-dominated throughout the study because of wind forcing and high volumes of water entering the northern Bay from the Atchafalaya River. Flushing time of the Bay averaged <8 days; however, more rapid flushing occurred in response to northerly winds with approximately 56% of the volume of the Bay exported to the Gulf in 1 day during the strongest flushing event. Higher nitrate+nitrite (NO₂+NO₃), total nitrogen (TN), and total phosphorus (TP) concentrations were indicative of Atchafalaya River input and fluxes were greater when influenced by high velocity northerly winds associated with frontal passage. Net exports of NO₂+NO₃, TN, and TP were 43.5, 98.5, and 13.6 g s⁻¹, respectively, for the 89-day study. An average of 10.6 g s⁻¹ of ammonium (NH₄) was exported to the Gulf over the study; however, concentrations were lower when associated with riverine influence and wind-driven exports suggesting the importance of biological processes. Phosphate (PO₄) fluxes were nearly balanced over the study with fairly stable concentrations indicating a well-buffered system. The results indicate that the high energy subsidy provided by natural pulsing events such as atmospheric cold fronts and seasonal river discharge are efficient mechanisms of nutrient delivery to adjacent wetlands and nearshore coastal ecosystems and are important in maintaining coastal sustainability.     

Modeling the Population Effects of Hypoxia on Atlantic Croaker (<Emphasis Type="Italic">Micropogonias undulatus</Emphasis>) in the Northwestern Gulf of Mexico: Part 2—Realistic Hypoxia and Eutrophication

Quantifying the population-level effects of hypoxia on coastal fish species has been challenging. In the companion paper (part 1), we described an individual-based population model (IBM) for Atlantic croaker in the northwestern Gulf of Mexico (NWGOM) designed to quantify the long-term population responses to low dissolved oxygen (DO) concentrations during the summer. Here in part 2, we replace the idealized hypoxia conditions with realistic DO concentrations generated from a 3-dimensional water quality model. Three years were used and randomly arranged into a time series based on the historical occurrence of mild, intermediate, and severe hypoxia year types. We also used another water quality model to generate multipliers of the chlorophyll concentrations to reflect that croaker food can be correlated to the severity of hypoxia. Simulations used 100 years under normoxia and hypoxia conditions to examine croaker population responses to the following: (1) hypoxia with food uncoupled and coupled to the severity of hypoxia, (2) hypoxia reducing benthos due to direct mortality, (3) how much hypoxia would need to be reduced to offset decreased croaker food expected under 25 and 50% reduction in nutrient loadings, and (4) key assumptions about avoidance movement. Direct mortality on benthos had no effect on long-term simulated croaker abundance, and the effect of hypoxia (about a 25% reduction in abundance) was consistent whether chlorophyll (food) varied with hypoxia or not. Reductions in hypoxia needed with a 25% reduction in nutrient loadings to result in minimal loss of croaker is feasible, and the croaker population will likely do as well as possible (approach abundance under normoxia) under the 50% reduction in nutrient loadings. We conclude with a discussion of why we consider our simulation-based estimates of hypoxia causing a 25% reduction the long-term population abundance of croaker in the NWGOM to be realistic and robust.     

Forecasting Gulf’s hypoxia: The next 50 years?

This review discusses the use of hypoxia models in synthesizing the knowledge about the causes of Gulf of Mexico hypoxia, predicting the probable consequences of management actions, and building a consensus about the management of hypoxia. It also offers suggestions for future efforts related to simulating and forecasting Gulf hypoxia. The existing hypoxia models for the northern Gulf of Mexico range from simple regression models to complex three-dimensional simulation models, and they capture very different aspects of the physics, chemistry, and biology of this region. Several of these models were successfully calibrated to observations relevant for their process formulations and spatial-temporal scales. Available model results are compared to reach the consensus that large-scale hypoxia probably did not begin in the Gulf of Mexico until the mid 1970s, and that the 30% nitrogen load reduction that is called for by the Action Plan may not be sufficient to achieve its goal. The present models results suggest that a 40–45% reduction in riverine nitrogen load may be necessary to achieve the desired reduction in the areal extent of hypoxia. These model results underscore the importance of setting this goal as a running average because of significant interannual variability. Caution is raised for setting resource management goals without considering the long-term consequences of climate variability and change.