The Waitomo Caves attract approximately 500 000 tourists each year. A requirement of tourist cave management is that the partial pressure of carbon dioxide (PCO₂) is kept below levels that are: hazardous to the health of visitors, hazardous to the glowworms and other natural inhabitants, or potentially corrosive to speleothems. For the Glowworm Cave at Waitomo, the maximum permissible PCO₂ level is 2400 ppm. When exceeded, the tourist operators are required to close the cave. Ten years of monitoring data at the Glowworm Cave was analysed. Most of the variation in PCO₂ could be attributed to CO₂ respired by tourists, and the mixing of cave air with lower PCO₂ outside air. Occasionally, there were periods with high PCO₂ levels while the cave was closed to tourists. The main objective of this study was to investigate the potential role of the Waitomo Stream in contributing CO₂ to the Glowworm Cave atmosphere. Analysis of ten years of Glowworm Cave monitoring data showed that the 2400 ppm PCO₂ limit was, on average, exceeded five times each year, with a total of 48 events between 1998 and 2007. Of the PCO₂ limit exceedences, approximately 31% of events were largely driven by high tourist numbers; 27% of PCO₂ limit exceedences were mainly driven by increased discharge, rainfall, and/or a low temperature gradient between the cave and outside air, whilst 29% of the PCO₂ limit exceedences were due to a combination of tourists and increased discharge, rainfall, and/or a low temperature gradient. The remaining 13% of exceedences were unexplained by tourists or the factors investigated. It may be that the unexplained exceedences were due to the night time closure of the cave door, restricting air exchange. The PCO₂ of the Waitomo Stream was measured by equilibrating air with the streamwater within a closed loop. The air was passed continuously through an infrared gas analyser (IRGA). The streamwater PCO₂ typically ranged between 600 - 1200 ppm. Fluctuations in the PCO₂ of the Waitomo Stream coincided with PCO₂ fluctuations in the Glowworm Cave air, and under most conditions, the stream probably acted as a sink for cave air CO₂. However, following rainfall events, the stream PCO₂ increased, exceeding cave air PCO₂, thus acting as a source of CO₂ to the cave air. High stream PCO₂ often occurred at times when air flow through the cave was restricted, e.g. when the temperature gradient between the cave air and outside air was low, or stream levels were high, thus limiting air movement. The combination of high stream PCO₂ and a low temperature gradient increased the likelihood of high cave air PCO₂. Dripwater was measured to determine whether an increase in dripwater PCO₂ occurred in response to rainfall events. When rainfall events resulted in increased discharge, the dripwater PCO₂ sometimes increased (occasionally exceeding 5000 ppm), however the pattern was not consistent. The chemistry of the Waitomo and Okohua (Ruakuri) Streams was monitored with daily samples collected and analysed for major ions: HCO₃ -, Ca²⁺, Na⁺ and Mg²⁺, and δ¹³C stable isotope. The HCO₃ -, Ca²⁺, Na⁺ and Mg²⁺ concentrations in the streamwater decreased with increased discharge, presumably due to dilution. Increased discharge following rainfall events correlated with increasing PCO₂ in the Waitomo Stream, suggesting that soil atmosphere CO₂ dissolved in soil waters, and carried to the stream by saturated flow, was responsible for the streamwater PCO₂ increase. Ca in the stream showed both an increase and a decrease with respect to rainfall. Increased Ca in the stream occurred at times when the discharged waters were coming from the phreatic zone, and thus sufficient time had lapsed for CO₂ in the discharge waters to react with the limestone (carbonate dissolution reaction). Decreased Ca occurred when the infiltration and percolation of rainwater was rapid, and thus the streamwater was characterised by a higher PCO₂ and a lower Ca concentration, as insufficient time had lapsed for the discharge waters to equilibrate with the limestone. Increased negativity in the δ¹³C of the Waitomo and Ruakuri Streams coincided with increased discharge. During summer low flow, the δ¹³C of Waitomo Stream waters was -11.3‰, whereas during high stream discharge events, the δ¹³C dropped to -12 - -14‰. The δ¹³C of limestone is 0‰, the atmosphere is -7‰, and the soil atmosphere is reported to be about -24‰, thus the decrease in δ¹³C during high flow events supports the contention that soil atmosphere CO₂ is a likely source of the increased CO₂ in flood waters.

Thesis (M.Sc. Earth and Ocean Sciences and Chemistry)--University of Waikato, 2009. / Title from PDF cover (viewed October 2, 2009). Includes bibliographical references (p. 161-170)

Growth rates, δ18O and δ13C of five stalagmites from the west coasts of North and South Islands, New Zealand, provide records of millennial-scale climate variability over the last ~75 kyr. Thirty-five uranium-series ages were used to provide the chronology. δ18O of stalagmite calcite was influenced by changes in moisture source region, temperature and both δ18O and δ13C primarily display a negative relationship with rainfall. To assist interpretation of climatic signals δ18O profiles were adjusted for the ice-volume effect. Changes in these proxies reflect changes in the strength of the circumpolar westerly circulation and the frequency of southwesterly flow across New Zealand. MIS 4 was a period of wet and cool climate lasting from 67.7 to 61.3 kyr B.P., expressed in the stalagmites by an interval of strongly negative isotope ratios and increased growth rate. This contrasts with less negative δ18O and δ13C, and slow growth, interpreted as dry and cold climate, during much of MIS 2. This difference between MIS 2 and MIS 4 provides an explanation for why glacial moraines in the Southern Alps of MIS 4 age lie beyond those deposited during the last glacial maximum (MIS 2). Heinrich events, with the exception of H0 (the Younger Dryas), are interpreted from high-resolution South Island stalagmite HW05-3, from Hollywood Cave, West Coast, as times of wetter and cooler climate. Minima in δ18O and δ13C (wet periods) occurred at 67.7-61.0, 56-55, 50.5-47.5, 40-39, 30.5-29, 25.5-24.3 and 16.1-15. kyr B.P. matching Heinrich events H6-H1 (including H5a) respectively. This demonstrates a robust teleconnection between events in the North Atlantic and New Zealand climate. Minima in δ18O also occurred at similar times in less well-dated North Island stalagmite RK05-3 from Ruakuri Cave, Waitomo. Speleothems from low-latitudes have revealed that Heinrich events forced southerly displacement of the Intertropical Convergence Zone. This caused steepening of the temperature gradient across mid-southern latitudes, increased westerly circulation and resulted in wet conditions on the west coast of both islands. Immediately following H1 in the HW05-3 stable isotope profiles is another excursion to more negative isotopic values, suggesting wet and cold climate, lasting from 14.6 to 13.0 kyr B.P. Such a climate on the West Coast at this time has been previously suggested from glacier advance (e.g. Waiho Loop moraine) and decreased abundance of tall trees on the landscape. This event occurred too early to be a response to H0, but is synchronous with a return to cool climate in Antarctica. Thus West Coast climate appears to have been sensitive to changes in Antarctica as well as the North Atlantic. Isotopic minima (wet and cool climate) in South Island stalagmite GT05-5, which formed during the Holocene, first occurred 4.6 kyr B.P. This began a series of four oscillations in isotope ratios, the last terminating when the stalagmite was collected (2006). Onset of these oscillations is associated with initiation of ice advance in the Southern Alps, and beginning of the Neoglacial. The last oscillation displays enriched isotope ratios lasting from 1.2 to 0.8 kyr B.P. succeeded by depleted ratios lasting until 0.15 kyr B.P., mirroring the Medieval Climate Optimum and Little Ice Age, respectively, of European palaeoclimate records.