Spectrophotometric determination of pH in seawater off Taiaroa Head,Otago, New Zealand: Full-spectrum modelling and prediction of pCO2 levels

Accurate measurement of seawater pH has long been sought by marine chemists (for example: [Dickson, A.G. 1993a. The measurement of sea water pH. Marine Chemistry, 44, 131–142, Dickson, A.G. 1993b. pH buffers for sea water media based on the total hydrogen ion concentration scale. Deep-Sea Research, 40, 107–118; Zhang, 1996; Tapp, M., Hunter, K.A., Currie, K. and Macaskill, B. 2000. Apparatus of continuous-flow underway spectrophotometric measurement of surface water pH. Marine Chemistry 72(2–4), 193–202; Friis, K., Koetzinger, A., Wallace, D.W.R. 2004. Spectrophotometric pH measurement in the ocean: Requirements, design and testing of an autonomous charge-coupled device detector system. Limnology and Oceanography: Methods 2, 126–136]. Recently, such attempts have taken on greater significance as anthropogenic carbon dioxide emissions may create rapidly changing oceanic pH. Spectrophotometric techniques have been accepted generally as the best for determination of seawater pH. Here we report a new technique using thymol blue as the indicator dye and fitting the entire spectrum from 400 to 900 nm rather than measuring the absorbance values at only two or three points in the spectrum. This full-spectrum modelling enables a reduction in signal to noise over other techniques. In the laboratory, we find with seawater samples a pH precision increase of five-fold “within” a sample and seven-fold “between” samples when comparing the full spectrum to the three-point method of analysis [Zhang, H., Byrne, R.H. 1996. Spectrophotometric pH measurements of surface seawater at in-situ conditions: absorbance and protonation behaviour of thymol blue. Marine Chemistry 52, 17–25].     

Thinking of England and taking care: family building strategies and infant mortality in England and Wales, 1891-1911

"Debates concerning the origins and development of the late nineteenth- to early twentieth-century declines in marital fertility and infant mortality in England and Wales have been centred largely on the material provided by answers to the ?special' questions in the 1911 census. In their published form these figures have restricted researchers to an examination of large scale geographic and social class differences in the levels and rates of decline of the two phenomena. This paper outlines research conducted on a sample of individual census returns from the 1911 census. From this data it becomes clear that for Victorian and Edwardian England ?where one lived' was rather more important than ?who one was' in determining both family building strategies and the survival of those children born."     

Biological and Geochemical Record of Anthropogenic Impacts in Recent Sediments from Lake Pupuke, Auckland City, New Zealand

Frozen sediment cores from Lake Pupuke in Auckland City, New Zealand, contain a high resolution decadal to annual scale record of changing lake paleoenvironments and geochemistry that reflects changing landuse and hydrology in the catchment over the past c. 190 years. A reliable chronology is available from AMS ¹⁴C and ²¹⁰Pb dating of the sediments, with the timing of the older part of the record supported by the first appearance of pollen of introduced Pinus and Plantago lanceolata associated with European settlement of Auckland in the early 1840s. Diatom stratigraphy, sediment elemental and carbon isotope geochemistry reflect changes in sediment sources and lake conditions commensurate with European development of the Lake Pupuke catchment, in particular enhanced algal productivity controlled by the influx of nutrients after c. 1920 AD. Attempts to prevent nuisance algal blooms in 1933, 1934 and 1939 using CuSO₄ addition produced Cu spikes in the sediment that allowed confirmation of the accuracy of the ²¹⁰Pb chronology. Hence, the elemental and isotopic composition of the Lake Pupuke sediments reflect the timing of significant anthropogenic activities, rather than climatic variations, that have occurred within the watershed over the past c. 190 years. The comparison of records of land use change in the catchment with the multi-proxy record of changes in the sediments usually allowed unambiguous identification of the signatures of change and their causes.     

Geochemistry of Tertiary tholeiites and picrites from Qeqertarssuaq (Disko Island) and Nuussuaq, West Greenland with implications for the mineral potential of comagmatic intrusions

Tertiary continental flood basalts on Qeqertarssuaq and Nuussuaq in West Greenland contain ～3?km of picrites and variably contaminated tholeiites. The picrites are in the Naujánguit member of the Vaïgat Formation and they have 7–29?wt% MgO, La/Sm?=?0.9–2.1, and ¹⁴³Nd/¹⁴⁴Nd?=?0.51263–0.51307. They appear to have crystallised from high-Mg parental magmas (14.4–16.4?wt% MgO) with isotope and trace element ratios similar to recent Icelandic picrites. Discrete horizons of tholeiites, including the Asûk and?Kûgánguaq, have elevated SiO₂ (50–58 wt%), La/Sm?=?3–7, ⁸⁷Sr/⁸⁶Sr?=?0.70550–0.71224, and low ¹⁴³Nd/¹⁴⁴Nd?=?0.51234–0.51174. These lavas have low Cu and Ni abundances (typically 10–50?ppm Ni or Cu), and in the case of the Asûk on Qeqertarssuaq, they contain droplets of native iron. The low Cu and Ni contents are attributed to scavenging by magmatic sulphides formed in response to crustal contamination of picritic magmas. Two contamination trends are recognised, one to a sediment end-member with high Th/Nb and Archaean model Nd ages, and the other to a meta-igneous component with high La/Sm, low Th/Nb and Rb/Nb, and Proterozoic source ages. Overall, ²⁰⁶Pb/²⁰⁴Pb varies from 16.47–21.68. Both contamination trends are associated with low Cu and Ni, and high SiO₂, and it is argued that the magmatic sulphides were triggered by the increases in silica, rather than simply by the introduction of additional crustal-derived sulphur. Geochemically, the Asûk and Kûgánguaq rocks resemble the most contaminated Nadezhdinsky lavas of the Siberian Trap, which are widely regarded as the source of the Ni and Cu mineralisation in the giant Noril'sk deposits. Mass balance considerations indicate that the parental liquids to the contaminated magmas contained sufficient Ni, Cu, S and platinum group elements to form substantial magmatic sulphide deposits. However, unlike the lavas at Noril'sk, the contaminated (low Cu and Ni) West Greenland basalts are in isolated units with no evidence for a gradual recovery in Ni and Cu abundances with height in the lava column. Comparison with Noril'sk suggests that although significant quantities of metals were scavenged by sulphides in West Greenland, the metal contents of the sulphides may not have been upgraded by continued interaction with subsequent magma batches.     

Balancing trade‐off issues in land use change and the impact on streamflow and salinity management

The south‐west region of the Goulburn–Broken catchment in the south‐eastern Murray–Darling Basin in Australia faces a range of natural resource challenges. A balanced strategy is required to achieve the contrasting objectives of remediation of land salinization and reducing salt export, while maintaining water supply security to satisfy human consumption and support ecosystems. This study linked the Catchment Analysis Tool (CAT), comprising a suite of farming system models, to the catchment‐scale CATNode hydrological model to investigate the effects of land use change and climate variation on catchment streamflow and salt export. The modelling explored and contrasted the impacts of a series of different revegetation and climate scenarios. The results indicated that targeted revegetation to only satisfy biodiversity outcomes within a catchment is unlikely to have much greater impact on streamflow and salt load in comparison with simple random plantings. Additionally, the results also indicated that revegetation to achieve salt export reduction can effectively reduce salt export while having a disproportionately smaller affect on streamflows. Furthermore, streamflow declines can be minimized by targeting revegetation activities without significantly altering salt export. The study also found that climate change scenarios will have an equal if not more significant impact on these issues over the next 70 years. Uncertainty in CATNode streamflow predictions was investigated because of the effect of parameter uncertainty. Copyright © 2012 John Wiley & Sons, Ltd.     

Reach‐scale contributions of road‐surface sediment to the Honna River,Haida Gwaii,BC

Gravel road surfaces can be a major source of fine sediment to streams, yet their contribution to channel reach sediment balances remains poorly documented. To quantify the input of road surface material and to compare this input with natural sediment sources at the reach scale, suspended sediment dynamics was examined and a 16‐month sediment balance was developed for a ~35 channel‐width (approx. 425 m) reach of the Honna River, a medium‐size, road‐affected stream located in coastal British Columbia. Of the 105 ± 33 t of suspended material passing through the reach, 18 ± 6% was attributed to the road surface. The high availability of sediment on the road surface appears to limit hysteresis in road run‐off. During rainstorms that increase streamflow, road surface material composed 0.5–15% of sediment inputs during relatively dry conditions from April to the end of September and 5–70% through wetter conditions from October to the end of March, but our data do not show evidence of major sediment accumulation on the riverbed in the reach. A comparison of modelled sediment production on the road surface with observed yields from drainage channels suggests that (1) during low intensity rainfall, ditches and drainage channels may trap sediment from road run‐off, which is subsequently released during events of greater intensity, and/or (2) production models do not effectively describe processes, such as deposition or erosion of sediment in ditches, which control sediment transport and delivery. Our findings further emphasize the risk of unpaved roads in polluting river systems and highlight the continued need for careful road design and location away from sensitive aquatic environments. Copyright © 2016 John Wiley & Sons, Ltd.