Water column

Abstract: Denitrification occurs in essentially all river, lake, and coastal marine ecosystems that have been studied. In general, the range of denitrification rates measured in coastal marine sediments is greater than that measured in lake or river sediments. In various estuarine and coastal marine sediments, rates commonly range between 50 and 250 µmol N m−2 h−1, with extremes from 0 to 1,067. Rates of denitrification in lake sediments measured at near-ambient conditions range from 2 to 171 µmol N m−2 h−1. Denitrification rates in river and stream sediments range from 0 to 345 µmol N m−2 h−1. The higher rates are from systems that receive substantial amounts of anthropogenic nutrient input. In lakes, denitrification also occurs in low oxygen hypolimnetic waters, where rates generally range from 0.2 to 1.9 µmol N liter−1 d−1. In lakes where denitrification rates in both the water and sediments have been measured, denitrification is greater in the sediments. The major source of nitrate for denitrification in most river, lake, and coastal marine sediments underlying an aerobic water column is nitrate produced in the sediments, not nitrate diffusing into the sediments from the overlying water. During the mineralization of organic matter in sediments, a major portion of the mineralized nitrogen is lost from the ecosystem via denitrification. In freshwater sediments, denitrification appears to remove a larger percentage of the mineralized nitrogen. N2 fluxes accounted for 76–100% of the sediment-water nitrogen flux in rivers and lakes, but only 15–70% in estuarine and coastal marine sediments. Benthic N2O fluxes were always small compared to N, fluxes. The loss of nitrogen via denitrification exceeds the input of nitrogen via N2 fixation in almost all river, lake, and coastal marine ecosystems in which both processes have been measured. Denitrification is also important relative to other inputs of fixed N in both freshwater and coastal marine ecosystems. In the two rivers where both denitrification measurements and N input data were available, denitrification removed an amount of nitrogen equivalent to 7 and 35% of the external nitrogen loading. In six lakes and six estuaries where data are available, denitrification is estimated to remove an amount of nitrogen equivalent to between 1 and 36% of the input to the lakes and between 20 and 50% of the input to the estuaries.

Abstract: The anoxic aquatic environment is a mass of water so depleted in oxygen that virtually all aerobic biologic activity has ceased. Anoxic conditions occur where the demand for oxygen in the water column exceeds the supply. Oxygen demand relates to surface biologic productivity, whereas oxygen supply largely depends on water circulation, which is governed by global climatic patterns and the Coriolis force. Organic matter in sediments below anoxic water is commonly more abundant and more lipid-rich than under oxygenated water mainly because of the absence of benthonic scavenging. The specific cause for preferential lipid enrichment probably relates to the biochemistry of anaerobic bacterial activity. Geochemical-sedimentologic evidence suggests that potential oil source beds are and have been deposited in the geologic past in four main anoxic settings as follows. 1. Large anoxic lakes: Permanent stratification promotes development of anoxic bottom water, particularly in large lakes which are not subject to seasonal overturn, such as Lake Tanganyika. Warm equable climatic conditions favor lacustrine anoxia and nonmarine oil source bed deposition. Conversely, lakes in temperate climates tend to be well oxygenated. 2. Anoxic silled basins: Only those landlocked silled basins with positive water balance tend to become anoxic. Typical are the Baltic and Black Seas. In arid-region seas (Red and Mediterranean Seas), evaporation exceeds river inflow, causing negative water balance and well-oxygenated bottom waters. Anoxic conditions in silled basins on oceanic shelves also depend upon overall climatic and water-circulation patterns. Silled basins should be prone to oil source bed deposition at times of worldwide transgression, both at high and low paleolatitudes. Silled-basin geometry, however, does not automatically imply the presence of oil source beds. 3. Anoxic layers caused by upwelling: These develop only when the oxygen supply in deep water cannot match demand owing to high surface biologic productivity. Examples are the Benguela Current and Peru coastal upwelling. No systematic correlation exists between upwelling and anoxic conditions because deep oxygen supply is often sufficient to match strongest demand. Oil source beds and phosphorites resulting from upwelling are present preferentially at low paleolatitudes and at times of worldwide transgression. 4. Open-ocean anoxic layers: These are present in the oxygen-minimum layers of the northeastern Pacific and northern Indian Oceans, far from deep, oxygenated polar water sources. They are analogous, on a reduced scale, to worldwide "oceanic anoxic events" which occurred at global climatic warmups and major transgressions, as in Late Jurassic and middle Cretaceous times. Known marine oil source bed systems are not randomly distributed in time but tend to coincide with periods of worldwide transgression and oceanic anoxia. Geochemistry, assisted by paleogeography, can greatly help petroleum exploration by identifying paleoanoxic events and therefore widespread oil source bed systems in the stratigraphic record. Recognition of the proposed anoxic models in ancient sedimentary basins should help in regional stratigraphic mapping of oil shale and oil source beds.

Abstract: A high-profile Royal Society report in 2005, followed by similar reports worldwide, high-lighted the fact that relatively little is known about the ecosystem effects of ocean acidification. Work to date has been largely limited to short-term experiments on isolated aspects of marine communities. Hall-Spencer et al. adopted an alternative approach, tracking the response to CO2 release from volcanic vent sites off the island of Ischia in the Bay of Naples, where ocean acidification has prevailed perhaps for centuries. Typical rocky shore communities rich in calcareous organisms thrive at normal pH, shifting to communities lacking scleractinian corals and low in sea urchin and algal numbers at low pH. The results show that such sites can act as natural experiments against which to test laboratory and modelled predictions of the effects of ocean acidification. The ecological impact of ocean acidification as a result of climate change is difficult to predict. A natural CO2 venting site is used here to demonstrate the shifts occurring in a rocky shore marine community as a result of a pH gradient. The atmospheric partial pressure of carbon dioxide ( ) will almost certainly be double that of pre-industrial levels by 2100 and will be considerably higher than at any time during the past few million years1. The oceans are a principal sink for anthropogenic CO2 where it is estimated to have caused a 30% increase in the concentration of H+ in ocean surface waters since the early 1900s and may lead to a drop in seawater pH of up to 0.5 units by 2100 (refs 2, 3). Our understanding of how increased ocean acidity may affect marine ecosystems is at present very limited as almost all studies have been in vitro, short-term, rapid perturbation experiments on isolated elements of the ecosystem4,5. Here we show the effects of acidification on benthic ecosystems at shallow coastal sites where volcanic CO2 vents lower the pH of the water column. Along gradients of normal pH (8.1–8.2) to lowered pH (mean 7.8–7.9, minimum 7.4–7.5), typical rocky shore communities with abundant calcareous organisms shifted to communities lacking scleractinian corals with significant reductions in sea urchin and coralline algal abundance. To our knowledge, this is the first ecosystem-scale validation of predictions that these important groups of organisms are susceptible to elevated amounts of . Sea-grass production was highest in an area at mean pH 7.6 (1,827 μatm ) where coralline algal biomass was significantly reduced and gastropod shells were dissolving due to periods of carbonate sub-saturation. The species populating the vent sites comprise a suite of organisms that are resilient to naturally high concentrations of and indicate that ocean acidification may benefit highly invasive non-native algal species. Our results provide the first in situ insights into how shallow water marine communities might change when susceptible organisms are removed owing to ocean acidification.

Abstract: The purpose of this review paper is to present the technical basis for establishing sediment quality criteria using equilibrium partitioning (EqP). Equilibrium partitioning is chosen because it addresses the two principal technical issues that must be resolved: the varying bioavailability of chemicals in sediments and the choice of the appropriate biological effects concentration. The data that are used to examine the question of varying bioavailability across sediments are from toxicity and bioaccumulation experiments utilizing the same chemical and test organism but different sediments. It has been found that if the different sediments in each experiment are compared, there is essentially no relationship between sediment chemical concentrations on a dry weight basis and biological effects. However, if the chemical concentrations in the pore water of the sediment are used (for chemicals that are not highly hydrophobic) or if the sediment chemical concentrations on an organic carbon basis are used, then the biological effects occur at similar concentrations (within a factor of two) for the different sediments. In addition, the effects concentrations are the same as, or they can be predicted from, the effects concentration determined in water- only exposures. The EqP methodology rationalizes these results by assuming that the partitioning of the chemical between sediment organic carbon and pore water is at equilibrium. In each of these phases, the fugacity or activity of the chemical is the same at equilibrium. As a consequence, it is assumed that the organism receives an equivalent exposure from a water-only exposure or from any equilibrated phase, either from pore water via respiration, from sediment carbon via ingestion; or from a mixture of the routes. Thus, the pathway of exposure is not significant. The biological effect is produced by the chemical activity of the single phase or the equilibrated system. Sediment quality criteria for nonionic organic chemicals are based on the chemical concentration in sediment organic carbon. For highly hydrophobic chemicals this is necessary because the pore water concentration is, for those chemicals, no longer a good estimate of the chemical activity. The pore water concentration is the sum of the free chemical concentration, which is bioavailable and represents the chemical activity, and the concentration of chemical complexed to dissolved organic carbon, which, as the data presented below illustrate, is not bioavailable. Using the chemical concentration in sediment organic carbon eliminates this ambiguity. Sediment quality criteria also require that a chemical concentration be chosen that is sufficiently protective of benthic organisms. The final chronic value (FCV) from the U.S. Environmental Protection Agency (EPA) water quality criteria is proposed. An analysis of the data compiled in the water quality criteria documents demonstrates that benthic species, defined as either epibenthic or infaunal species, have a similar sensitivity to water column species. This is the case if the most sensitive species are compared and if all species are compared. The results of benthic colonization experiments also support the use of the FCV. Equilibrium partitioning cannot remove all the variation in the experimentally observed sediment- effects concentration and the concentration predicted from water-only exposures. A variation of approximately a factor of two to three remains. Hence, it is recognized that a quantification of this uncertainty should accompany the sediment quality criteria. The derivation of sediment quality criteria requires the octanol/water partition coefficient of the chemical. It should be measured with modern experimental techniques, which appear to remove the large variation in reported values. The derivation of the final chronic value should also be updated to include the most recent toxicological information.