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Notice Concerning Copyright Restrictions NOTICE CONCERNING COPYRIGHT RESTRICTIONS This document may contain copyrighted materials. These materials have been made available for use in research, teaching, and private study, but may not be used for any commercial purpose. Users may not otherwise copy, reproduce, retransmit, distribute, publish, commercially exploit or otherwise transfer any material. The copyright law of the United States (Title 17, United States Code) governs the making of photocopies or other reproductions of copyrighted material. Under certain conditions specified in the law, libraries and archives are authorized to furnish a photocopy or other reproduction. One of these specific conditions is that the photocopy or reproduction is not to be "used for any purpose other than private study, scholarship, or research." If a user makes a request for, or later uses, a photocopy or reproduction for purposes in excess of "fair use," that user may be liable for copyright infringement. This institution reserves the right to refuse to accept a copying order if, in its judgment, fulfillment of the order would involve violation of copyright law. CHAPTER IX Chemical Investigations at Waiotapu By S. H. WILSON, INSTITUTE OF NUCLEAR SCIENCES, LoWER HuTT. INTRODUCTION From the chemical work on the discharges of the holes at Wairakei, it had become clear that these were fed from a fairly uniform body of chloride water at a temperature of about 250°c. After the opening of any hole there is a very variable initial period of about one year during which the chloride content is approximately 25 % lower, but finally the chloride content becomes almost constant. There are small variations from hole to hole, but it appears that these can be explained on the hypothesis that originally there was water of uniform enthalpy and chloride content, and there have been variable changes in enthalpy and chloride content by dilution with cold water, loss of heat as steam or by conduction, or drawing of excess steam into the hole discharge. On account of this variation it is best to express the other constituents in the form of ratios to chloride or to sodium. At Wairakei it has been found that certain ratios are fairly constant over the whole field, and this .fact reinforces the deduction from the chloride content, of a body of water of uniform composition, at least originally. The ratios that are practically constant are those of chloride to fluoride, to boric acid, and to arsenic. lt. is also easy to determine these ratios accurately as all four constituents are present only in the water fraction of the discharge. There are three other ratios that' are more difficult to determine because three of the constituents are present in the discharge in both the water and the steam fractions. It is necessary to sample steam and water separately, and to calculate the composition of the original steam-free water phase. With separate sampling of steam and water, it has been difficult to eliminate various sources of error in the calculated composition of the, original water phase. The ratios of chloride to total carbon dioxide (i.e., carbon dioxide present in the steam as gas, in the water as carbon dioxide, and as bicarbonate) and of chloride to total sulphur (i.e., sulphur present in the steam as hydrogen sulphide and in the water as sulphate) seem also to be constant for the deeper bores of normal enthalpy, but there are considerable differences associated with differences in the enthalpies of the hole discharges. Where the underground water has cooled by loss of steam, much carbcn dioxide and hydrogen sulphide is carried off with the steam. Ammonia is another constituent that is determined in both water and condensed-steam samples. The ratio of chloride to ammonia is quite variable. It is low in the shallow holes just penetrating the impermeable Huka beds, but high in the holes deeper in the Waiora breecia or drawing from fissures in the ignimbrite. More useful, and more easily determined (for the constituents are both entirely 87 in the water phase) is the ratio of sodium to potassium. This is high in the waters from shallow holes and still fairly high in waters from holes tapping hot water in the "permeable volcanics" where apparently time of contact or the greater surface available has permitted potassium to replace sodium to a considerable extent in feldspar minerals. In the deeper holes in the western part of the area, where these have tapped fissures in the ignimbrite, sodium/potassium ratios have been as low as 9·5. The realisation that the holes were fed from a fairly uniform body of chloride water led to a better understanding of the natural activity. There are two main hot-spring areas at Wairakei - the Waiora and Geyser Valleys. Waiora Valley is an area of acid sulphate and mixed chloride-sulphate waters. The waters seem to be surface water heated by steam rising up from chloride water below, although in springs in the lower part of the valley there is some admixture with chloride water. Although the area is close to the locality where the most successful holes have been drilled, the composition of the spring waters is of no help in indicating the character of the hot chloride water below. At Geyser Valley, however, the outflow of hot chloride water is very much greater. Analyses of the spring waters have shown that the ratios of chloride to fluoride, boric acid, and arsenic, are much the same as those for waters from the holes. The chloride content of the waters is somewhat lower than that in water separ- ated at amospheric pressure from the hole discharges. It could be explained by admixture with about 20% of cold water. The sodium/potassium ratio is somewhat higher than the ratio generally found in waters from holes in the permeable volcanics. lt appears that the hot chloride springs at Geyser Valley are supplied from the hot water discovered by drilling. The main changes are that a large amount of steam, and with it most of the gas, escapes from the water, some of it in the hot pools and geysers, and there is some admixture with cold water before the hot water reaches the springs. By far the largest spring is the Champagne Cauldron, which contributes about 50 % of the heat supplied to the stream draining the area. The water of this spring is less diluted with cold water than any other spring. Ifthere had been no drilling in the Wairakei locality it would have been possible to obtain a good idea of the character of the under- ground "primary chloride water" from the analysis of the water of Champagne Cauldron. Owing to the loss in the steam of carbon dioxide, hydrogen sulphide, and ammonia, it is not possible to get any information as to the content of these constituents in the underground chloride water. When it was appreciated that in most thermal areas the surface activity is due to steam and water coming up from "primary chloride water", probably of uniform composition in each area, it became of interest to take water samples in other thermal areas in the Rotorua-Taupo region in order to check this hypothesis, and to determine what differences there were in the characteristic ratios in the various thermal areas. Sampling for this purpose was carried out in 1955. The aim was to take samples from the springs of highest flow and chloride content. Previous sampling was not always a guide, as the most striking pools or the most vigorously boiling were not always those required. In some cases, as at Geyser Valley, 88 one spring had a flow so much greater than the others that it alone was worth sampling. 1n other cases, a number of springs had to be sampled, and by judgment from the general agreement of the ratios, a decision had to be reached as to whether they were fed from one uniform body of underground chloride water. It should be pointed out that difficulties are caused by the occurrence of waters of mixed origin, i.e., those formed by mixing of chloride water with surface water heated by steam. This steam carries no chloride, a small amount of ammonia, and very small amounts of boric acid and hydrogen fluoride. If the mixed water con- tains some surface water heated by steam, the chloride/ammonium ratio can be considerably lowered, but the chloride/fluoride and chloride/boric acid ratios would be hardly affected. The fact that waters considered to be of mixed. origin have low chloride/fluoride and chloride/boric-acid ratios indicates that the water has either scrubbed the ammonia, boric acid, and fluoride from a large amount of steam passing through it, or else has leached these constituents from ground in which they had previously been absorbed from steam. These waters are generally high in sulphate, formed by the oxidation near the surface of hydrogen sulphide in the steam. Such waters must be distinguished from the true chloride waters, as the ratios of the constituents give no clue to the characteristic ratios of the "primary chloride water". The result of the investigation was to confirm the belief that in most thermal areas the activity was due to the presence underground of"primary chloride water", and to show that each area had characteristic constituent ratios, differing very considerably from area to area. NATURAL ACTIVITY AT WAIOTAPU The samples of the waters of hot springs at Waiotapu were taken in June 1955 as part of theprogramme of sampling the springs of hot chloride water in the whole thermal region. At Waiotapu, the aim was to make a representative sampling of the active area by taking three samples of springs of high temperature and good flow.
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