Limitations of the ferrozine method for quantitative assay of mineral systems for ferrous and total iron

The quantitative assay of clay minerals, soils, and sediments for Fe(II) and total Fe is fundamental to understanding biogeochemical cycles occurring therein. The commonly used ferrozine method was originally designed to assay extracted forms of Fe(II) from non-silicate aqueous systems. It is becoming, however, increasingly the method of choice to report the total reduced state of Fe in soils and sediments. Because Fe in soils and sediments commonly exists in the structural framework of silicates, extraction by HCl, as used in the ferrozine method, fails to dissolve all of the Fe. The phenanthroline (phen) method, on the other hand, was designed to assay silicate minerals for Fe(II) and total Fe and has been proven to be highly reliable. In the present study potential sources of error in the ferrozine method were evaluated by comparing its results to those obtained by the phen method. Both methods were used to analyze clay mineral and soil samples for Fe(II) and total Fe. Results revealed that the conventional ferrozine method under reports total Fe in samples containing Fe in silicates and gives erratic results for Fe(II). The sources of error in the ferrozine method are: (1) HCl fails to dissolve silicates and (2) if the analyte solution contains Fe³⁺, the analysis for Fe²⁺ will be photosensitive, and reported Fe(II) values will likely be greater than the actual amount in solution. Another difficulty with the ferrozine method is that it is tedious and much more labor intensive than the phen method. For these reasons, the phen method is preferred and recommended. Its procedure is simpler, takes less time, and avoids the errors found in the ferrozine method.     

The hydrochemistry of a semi-arid pan basin case study: Sua Pan,Makgadikgadi, Botswana

This study presents results on the fluid and salt chemistry for the Makgadikgadi, a substantial continental basin in the semi-arid Kalahari. The aims of the study are to improve understanding of the hydrology of such a system and to identify the sources of the solutes and the controls on their cycling within pans. Sampling took place against the backdrop of unusually severe flooding as well as significant anthropogenic extraction of subsurface brines. This paper examines in particular the relationship between the chemistry of soil leachates, fresh stream water, salty lake water, surface salts and subsurface brines at Sua Pan, Botswana with the aim of improving the understanding of the system’s hydrology. Occasionally during the short wet season (December–March) surface water enters the saline environment and precipitates mostly calcite and halite, as well as dolomite and traces of other salts associated with the desiccation of the lake. The hypersaline subsurface brine (up to TDS 190,000 mg/L) is homogenous with minor variations due to pumping by BotAsh mine (Botswana Ash (Pty) Ltd.), which extracts 2400 m³ of brine/h from a depth of 38 m. Notable is the decrease in TDS as the pumping rate increases which may be indicative of subsurface recharge by less saline water. Isotope chemistry for Sr (⁸⁷Sr/⁸⁶Sr average 0.722087) and S (δ³⁴S average 34.35) suggests subsurface brines have been subject to a lithological contribution of undetermined origin. Recharge of the subsurface brine from surface water including the Nata River appears to be negligible.     

Monitoring Large-Scale Tests for Nuclear Waste Disposal

Two large-scale “in situ” demonstration experiments and their instrumentation are described. The first test (FEBEX Experiment) involves the hydration of a compacted bentonite barrier under the combined effect of an inner source of heat and an outer water flow from the confining saturated granite rock. In the second case, the progressive de-saturation of Opalinus clay induced by maintained ventilation of an unlined tunnel is analyzed. The paper shows the performance of different sensors (capacitive cells, psychrometers, TDR’s) and a comparison of fill behaviour with modelling results. The long term performance of some instruments could also be evaluated specially in the case of FEBEX test. Capacitive sensors provide relative humidity data during long transient periods characterised by very large variations of suction within the bentonite.     

THE DELINEATION OF THE BEDROCK CONFIGURATION OF PART OF PORT JACKSON,NEW SOUTH WALES,WITH A BOOMER SYSTEM*

A high resolution Boomer system was used to investigate the bedrock configuration of part of Port Jackson, New South Wales. The continuous reflection profiling technique was successful in delineating a channel incised in bedrock under a thickness of up to 60 m. of unconsolidated sediment covered by up to 20 m. of water.     

THE AIR PHOTOGRAPH REQUIREMENTS OF GEOLOGISTS

The geologist's use of air photographs and the characteristics studied by photogeologists are briefly described. The influence of photographic factors such as scale, season, time of day, film type, processing, overlap and dimensional accuracy are considered from the geologist's viewpoint.     

THE ANALYTICAL ORIENTATION OF A LUNAR MODEL

An analytical relative orientation of a stereo-pair of photographs was computed in an unusual system of co-ordinates. The disparity in the widely mismatched photographs, their tilts and narrow angles subtended resulted in a rather weak solution from which sections of the lunar surface have been plotted. The results were not good but were better than expected. The main outcome of the work is a, probably unique, demonstration of the versatility of analytical photogrammetry.