The effects of sea salts on the forms of nitrogen released from estuarine and freshwater sediments: Does ion pairing affect ammonium flux?

In sediments with oxidized surface layers, the percentage of mineralized nitrogen that is nitrified/denitrified, compared with that released directly as ammonium, appears to be affected by the presence of sea salts. In estuarine systems, a significant portion of the nitrogen is released as ammonium, whereas in freshwater systems, most of the mineralized nitrogen is often released from the sediments as nitrogen gas. We hypothesized that this discrepancy is caused by differential competition between physical diffusion and nitrification/denitrification in the two systems. The vertical migration (by Fickian diffusion) of ammonium out of the oxic layer may be hindered by cation exchange (or sorption) interactions with sediment particles to a greater extent in fresh water than in estuarine systems. The resulting relatively long residence time, and potentially high levels of particle-bound ammonium in the freshwater sediments, would favor nitrification as the major ammonium removal process. By contrast, ion pair formation of ammonium with seawater anions and blockage of sediment cation exchange sites with seawater cations may allow a sizable fraction of the ammonium to diffuse out of estuarine sediments before it is nitrified. A salt effect, consistent with this hypothesis, has been demonstrated in experimental systems by changing the ionic composition of water flowing above intact cores of freshwater and estuarine sediments. Steady-state ammonium release from Lake Michigan sediments was substantially enhanced in the presence of 30% seawater over that in the presence of lake water alone. Likewise, steady-state ammonium release, from Ochlockonee River and Bay sediments (Florida) and from Toms River and Barnegat Bay sediments (New Jersey), was usually higher in the presence of diluted synthetic seawater than it was in the presence of fresh water.     

Laboratory spectroscopic studies of atmospherically important radicals using fourier transform spectroscopy

This paper describes laboratory experiments designed to obtain the infrared spectra of some atmospherically important radical species and related compounds. A Fourier transform spectrometer was used that was capable of yielding resolutions as great as 0.0024 cm^-1, and optical paths of up to 512 m were employed. The objective of the experiments was to obtain the spectra for subsequent application to remote sounding measurements in the atmosphere.Radicals were generated by a variety of chemical reactions involving atoms or other highly reactive precursors. Spectra of the ₃ band of NO₃, at ca. 1500 cm^-1, were obtained with up to 0.005 cm^-1 resolution using the reaction between NO₂ and O₃ to produce the radical. The most satisfactory source of ClO was found to be the reaction between Cl and O₃, and the (1-0) vibration-rotation band in the region 829–880 cm^-1 was recorded at a resolution of 0.02 cm^-1. We were unable to observe infrared absorption of HO₂ with any of the radical sources that we tested. High-resolution survey spectra were obtained of compounds used as reactants, or formed as side-products in the radical-generating processes. These compounds included N₂O₅, HNO₃, ClONO₂, FNO₂, Cl₂O, HO₂NO₂, and probably FO₂.The ability to monitor concentrations of the NO₃ radical in the visible region of the spectrum as well as the concentrations of reactants and other products in the infrared region allowed us to undertake a study of the time-dependent interactions occurring when NO₂ reacts with O₃. The results indicate the importance of heterogeneous processes, especially when traces of water are present, and lend credence to suggestions that heterogeneous mechanisms in the NO₃–N₂O₅–H₂O system might be a viable source of HNO₃ in the atmosphere.     

The influence of surface cover and climate on energy partitioning and evaporation in a subarctic wetland

Energy partitioning and evaporation were measured over three wetland surfaces in a subarctic coastal marsh during pre-growing and growing periods. These surfaces included an alder/willow woodland, a sedge marsh and a raised backshore sedge meadow. A combination model analysis was used to assess the relative importance of surface resistance and meteorological conditions on the magnitude of the Bowen ratio, , during the growing period.Overall, the three surfaces experienced important site-to-site and seasonal differences in and evaporation, Q _E. During the non-foliated period, Q _E was largest and was smallest for the open water marsh, while the dry backshore site experienced the smallest Q _E and largest . The non-foliated woodland assumed intermediate values of and Q _E. After the vegetation covers were established, the woodland assumed the smallest and largest Q _E flux. It was also found that at the marsh site increased with the presence of a vegetation cover.Wind direction was always an important factor in determining Q _E and at all sites. was substantially larger and Q _E was smaller for onshore winds (i.e., originating from James Bay) than for offshore winds. The combination model analysis showed that canopy resistance at all sites was largest during warm offshore winds, which were associated with large saturation deficits. However, the effect of increased canopy resistance on during offshore winds was offset by a large climatological resistance, resulting in small values and large Q _E. When winds originated from James Bay, canopy resistance was smaller than for offshore winds, but the climatological resistance also was much smaller, resulting in larger and small Q _E. The results have important implications for changes in land cover and climate on the regional water balance.     

Heavy metal migration at a landfill site, Sarnia, Ontario, Canada—2: metal partitioning and geotechnical implications

Heavy metal profiles below a 15-year old sanitary landfill overlying a 30 m thick natural clay deposit are presented. Results indicate that unlike soluble species such as Cl⁻ and Na⁺ which have migrated distances up to 130 cm, Cu, Zn and Pb have migrated only up to 10 cm. The extent of Fe migration is estimated to be 20 cm. Highly reducing conditions at the interface (E_h= −130mV), coupled with the alkaline nature of the clay pore waters, have resulted in the precipitation of migrated heavy metals as carbonates. At the clay/waste interface, 88, 84 and 80% of the excess Fe, Zn and Pb, respectively, are present as secondary carbonates. This is confirmed by selective chemical dissolution analyses which also show that Fe, Zn, Pb and, to a greater extent, Cu are present in solid organic forms at the interface. Batch equilibrium studies clearly show that Cu and Pb removal from leachate is significantly increased by the presence of carbonates in the soil. For example, 75% more Pb is removed by the carbonate-rich bulk soil than the carbonate-free soil. The batch studies also show that when thepH> 5.2, removal of metal increases significantly due to precipitation as carbonates. From the results it is concluded that the presence of metal sludges in landfills lined naturally or artifically by a carbonate-rich clayey barrier reduces the rate of migration of numerous toxic transition metals and may also decrease the barrier porosity by precipitation. The decreases in porosity will be beneficial to the performance of the barrier due to reductions in both advection and diffusion.     

Short‐term microscale topographic changes of coastal bedrock on shore platforms

We report a series of short‐term (diurnal) rock surface monitoring studies on inter‐ and supra‐tidal shore platforms using a traversing micro‐erosion meter at two sites, Kaikoura Peninsula, New Zealand, and Apollo Bay, Victoria, Australia. Statistically signi?cant day‐to‐day changes were measured. Surface rise and lowering occurred at rates above instrument error, with a maximum range of 3·378 mm between 1·697 mm (lowering) and ‐1·681 mm (rise). Individual measurements showed rises greater than 2 mm. These daily variations reveal that surface lowering and rise occur at a much shorter time scale than previously reported from other studies. The patterns observed suggest wetting and drying is the most likely process causing surface changes at these temporal scales. We argue that traversing micro‐erosion meter studies operating at a short‐term time scale of day‐to‐day provide meaningful results that open new opportunities for studying rock weathering and erosion in a coastal environment. Copyright © 2004 John Wiley & Sons, Ltd.     

Gully Initiation and Implications for Management of Scour Holes in the Vicinity of the Jabiluka Mine, Northern Territory, Australia

A track across a burnt grass swale was used intensively on the Jabiluka Mineral Lease (located adjacent to Kakadu National Park in the seasonally wet tropics of the Northern Territory, Australia) for a short time period during the 1998 dry season. Repeated vehicle passes over the burnt grass increased soil bulk density and locally disrupted the root and algal mat, lowering the critical shear stress for sediment transport. Overland flow during the next wet season was above average and eroded eleven discontinuous, flow‐aligned scour holes in the wheel ruts where the track crossed grassed sandy swales. Although the site was burnt again during the next dry season, the scour holes did not coalesce during the second wet season, which was wetter than the previous one, because infrequent traffic bypassed the eroded section allowing grass to re‐establish. Scour holes on vehicle tracks in the Kakadu region are an intermediate but reversible stage in the development of gullies in grassed swales. Treatment of scour holes by soil conservation works may prevent gully formation.     

Laboratory Kinetic Studies of the Reactions of Cl Atoms with Species of Biogenic Origin: δ3-Carene, Isoprene, Methacrolein and Methyl Vinyl Ketone

The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10^-10, (2.1 ± 0.5) × 10^-10, (3.2 ± 0.5) × 10^-10, and (4.9 ± 0.5) × 10^-10 cm³ molecule^-1 s^-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and ³-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.     

Cyprus umbers: Chemical precipitates on a Tethyan ocean ridge

Iron-rich mudstones (umbers), directly overlying pillow lavas of the Troodos Massif, Cyprus, are interpreted as precipitates connected with late stages of volcanism on a Cretaceous ocean ridge. Chemical composition of the basal sediments allies them with the basal iron-rich sediments of the East Pacific Rise. Overlying radiolarites and chalks are more comparable to normal pelagic sediments. Sedimentary features and stratigraphic relations suggest rapid deposition of umbers, relative to the overlying sediments.