Iron and Sulfur Chemistry in a Stratified Lake: Evidence for Iron-Rich Sulfide Complexes

A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment. Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as [Fe(H₂O)₆]²⁺ or free H₂S as H₂S/HS^- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H₂S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe₂SH³⁺ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom waters are similar to the pK_sp of mackinawite. Soluble iron-sulfide species are stable in the absence of O₂ (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes can react with O₂ to oxidize sulfide and can also dissociate releasing volatile H₂S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/gr_{dry wt}) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich sulfide complexes.     

Characterization of permineralized kerogen from an Eocene fossil fern

The processes of organic maturation that occur during the permineralization of fossils and the detailed chemistry of the resulting products are incompletely understood. Primary among such processes is the geochemical alteration of biological matter to produce kerogen, such as that which comprises the cell walls of the fossils studied here: essentially unmetamorphosed, Eocene plant axes (specimens of the fossil fern Dennstaedtiopsis aerenchymata cellularly permineralized in cherts of the Clarno Formation of Oregon and the Allenby Formation of British Columbia). The composition and molecular structure of the kerogen that comprises the cell walls of such axes were analyzed using ultraviolet Raman spectroscopy (UV–Raman), solid state ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR) and pyrolysis–gas chromatography–mass spectrometry (py–GC–MS).Cellularly well-preserved fern axes from both geologic units exhibit similar overall molecular structure, being composed primarily of networks of aromatic rings and polyene chains that, unlike more mature kerogens, lack large polycyclic aromatic hydrocarbon (PAH) constituents. The cell walls of the Allenby Formation specimens are, however, less altered than those of the Clarno chert, exhibiting more prevalent oxygen-containing and alkyl functional groups and comprising a greater fraction of rock mass.The study represents the first demonstration of the effectiveness (and limitations) of the combined use of UV–Raman, ¹³C NMR and py–GC–MS for the analysis of the kerogenous cell walls of chert-permineralized vascular plants.     

U.S. Minerals Management Service (MMS) Prelease Geological and Geophysical (G & G) Data Acquisition: A 20-Year Retrospective, 1976-1996

Since 1976, the Minerals Management Service (MMS) has administered its prelease geological and geophysical (G & G) data acquisition program through Title 30, Part 251, of the Code of Federal Regulations, which govern permitting, acquisitions, and data release. Leading indicators of offshore oil and gas activity are the number of permits issued to industry, associated mileage, and expenditures. Over the last 20 years, permit activity has indicated that most of the oil and gas surveying has been in the Gulf of Mexico, where 80 % of all permits have been issued, followed by Alaska (10 %), the Pacific (7 %), and the Atlantic (3 %). These statistics correlate with the dominant position of the central and western Gulf of Mexico areas in oil and gas activity. More than 95 % of all permits were issued for geophysical exploration, mostly for two-dimensional (2-D) common-depth-point (CDP) seismic data. However, over the last 10 years, permits for three-dimensional (3-D) seismic data have averaged 25 % of all geophysical permits and, by 1996, made up approximately half of all geophysical permits offshore-wide. Between 1976 and the early 1990s, industry shot approximately 500,000 linemiles of 2-D CDP data each year on the Outer Continental Shelf (OCS). Of that total, MMS acquired approximately50,000 line-miles annually. In the 1990s, parallel with industry, MMS increased its acquisition of 3-D seismic data in concert with the development and use of interactive workstations. The majority of 2-D and 3-D data have been acquired in the Gulf of Mexico by a ratio of 2:1 over Alaska, the next largest data inventory. With regard to MMS expenditures for G & G data, from 1976 through the 1980s, Alaska, having more offshore area than the other three regions combined, had the largest portion. However, in the 1900s, the vast majority of expenditures have been in the Gulf of Mexico. Over the years, permit totals, mileage acquired, and expenditures for data reflect trends of oil and gas pricing, limitations of offshore moratoria, and a shift of industry emphasis to foreign theaters.     

Private rights,public benefits: Industry-driven seabed protection

New Zealand has a large exclusive economic zone (EEZ) that contains a variety of marine habitats and commercially-important species. The commercial fishing industry operating within New Zealand's EEZ is of significant value to the economy and fisheries resources are managed through the extensive use of Individual Transferable Quotas (ITQs). One of the benefits of ITQs has been to better align some of the private incentives of quota owners with the public interest. These incentives contributed to an initiative proposed by the fishing industry to close large areas of New Zealand's EEZ to protect the seabed from trawling. These closed areas are termed benthic protection areas (BPAs) and protect the benthic biodiversity of about 1.1 million square kilometres of seabed—approximately 30% of New Zealand's EEZ. A significant proportion of New Zealand's known seamounts and active hydrothermal vents are protected by these closed areas. We describe and discuss the criteria used to select BPAs and some of the criticism of this marine protection initiative. We argue that the assignment of strong property rights in fishing resources was an important precondition to an industry initiative that has a significant public benefit. Where private and public interests are well aligned, government can adopt an enabling and facilitation role, ceding direct control of processes in order to get the results the align with the public interest.     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.