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.     

Growing up green on serpentine soils: Biogeochemistry of serpentine vegetation in the Central Coast Range of California

Serpentine soils derived from the weathering of ultramafic rocks and their metamorphic derivatives (serpentinites) are chemically prohibitive for vegetative growth. Evaluating how serpentine vegetation is able to persist under these chemical conditions is difficult to ascertain due to the numerous factors (climate, relief, time, water availability, etc.) controlling and affecting plant growth. Here, the uptake, incorporation, and distribution of a wide variety of elements into the biomass of serpentine vegetation has been investigated relative to vegetation growing on an adjacent chert-derived soil. Soil pH, electrical conductivity, organic C, total N, soil extractable elements, total soil elemental compositions and plant digestions in conjunction with spider diagrams are utilized to determine the chemical relationships of these soil and plant systems. Plant available Mg and Ca in serpentine soils exceed values assessed in chert soils. Magnesium is nearly 3 times more abundant than Ca in the serpentine soils; however, the serpentine soils are not Ca deficient with Ca concentrations as high as 2235 mg kg⁻¹. Calcium to Mg ratios (Ca:Mg) in both serpentine and chert vegetation are greater than one in both below and above ground tissues. Soil and plant chemistry analyses support that Ca is not a limiting factor for plant growth and that serpentine vegetation is actively moderating Mg uptake as well as tolerating elevated concentrations of bioavailable Mg. Additionally, results demonstrate that serpentine vegetation suppresses the uptake of Fe, Cr, Ni, Mn and Co into its biomass. The suppressed uptake of these metals mainly occurs in the plants’ roots as evident by the comparatively lower metal concentrations present in above ground tissues (twigs, leaves and shoots). This research supports earlier studies that have suggested that ion uptake discrimination and ion suppression in the roots are major mechanisms for serpentine vegetation to tolerate the chemistry of serpentine soils.     

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.     

Pervasive wetland flooding in the glacial drift prairie of North Dakota (USA)

This article describes a unique flood hazard, produced by the dramatic expansion of wetlands in Nelson County, located within the North American Prairie Pothole Region of North Dakota, USA. There has been an unprecedented increase in the number, average size, and permanence of prairie wetlands, and a significant increase in the size of a closed lake (Stump Lake) due to a decade-long wet spell that began in 1993 following a prolonged drying trend. Base-line land cover information from the 1992 USGS National Land Cover Characterization dataset, and a Landsat TM scene acquired 9 July 2001 are used to assess the growth of the closed lake and wetland pond surface areas, and to analyze the type and area of various land cover classes inundated between 1992 and 2001. The open water profile in Nelson County changed from one marked by relatively comparable coverage of closed lake and wetland pond areas in 1992, to one in which wetland open water accounted for the vast majority of total open water in 2001. The bulk of the wetland pond area expansion occurred by displacing existing wetland vegetation and agricultural cropland. Producers responded to the flood hazard by filing Federal Crop Insurance Corporation (FCIC) claims and enrolling cropland in the Conservation Reserve Program (CRP), a federal land retirement program. Land taken out of agricultural production has had an enormous impact upon the agricultural sector that forms the economic base of the rural economy. In 2001 the land taken out of production due to CRP enrollment and preventive planting claims represented nearly 42% of Nelson County’s 205.2 K ha base agricultural land. The patterns obtained from this detailed study of Nelson County are likely to be the representative of the more publicized flood disaster occurring within the Devils Lake Basin of North Dakota.     

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.