Use of hierarchical cluster analysis to assess the representativeness of a baseline groundwater quality monitoring network: comparison of New Zealand’s national and regional groundwater monitoring programs

Baseline monitoring of groundwater quality aims to characterize the ambient condition of the resource and identify spatial or temporal trends. Sites comprising any baseline monitoring network must be selected to provide a representative perspective of groundwater quality across the aquifer(s) of interest. Hierarchical cluster analysis (HCA) has been used as a means of assessing the representativeness of a groundwater quality monitoring network, using example datasets from New Zealand. HCA allows New Zealand's national and regional monitoring networks to be compared in terms of the number of water-quality categories identified in each network, the hydrochemistry at the centroids of these water-quality categories, the proportions of monitoring sites assigned to each water-quality category, and the range of concentrations for each analyte within each water-quality category. Through the HCA approach, the National Groundwater Monitoring Programme (117 sites) is shown to provide a highly representative perspective of groundwater quality across New Zealand, relative to the amalgamated regional monitoring networks operated by 15 different regional authorities (680 sites have sufficient data for inclusion in HCA). This methodology can be applied to evaluate the representativeness of any subset of monitoring sites taken from a larger network.

Nitrate reduction over nanoscale zero-valent iron prepared by hydrogen reduction of goethite

Nitrate reduction with nanoscale zero-valent iron (NZVI) was reported as a potential technology to remove nitrate from nitrate-contaminated water. In this paper, nitrate reduction with NZVI prepared by hydrogen reduction of natural goethite (NZVI-N, -N represents natural goethite) and hydrothermal goethite (NZVI-H, -H represents hydrothermal goethite) was conducted. Besides, the effects of reaction time, nitrate concentration, iron-to-nitrate ratio on nitrate removal rate over NZVI-H and NZVI-N were investigated. To prove their excellent nitrate reduction capacities, NZVI-N and NZVI-H were compared with ordinary zero-valent iron (OZVI-N) through the static experiments. Based on all above investigations, the mechanism of nitrate reduction with NZVI-N was proposed. The result showed that reaction time, nitrate concentration, iron-to-nitrate ratio played an important role in nitrate reduction by NZVI-N and NZVI-H. Compared with OZVI, NZVI-N and NZVI-H showed little relationship with pH. And NZVI-N for nitrate composition offers a higher stability than NZVI-H because of the existence of Al-substitution. Furthermore, NZVI-N, prepared by hydrogen reduction of goethite, has higher activity for nitrate reduction and the products contain hydrogen, nitrogen, NH 4 +, a little nitrite, but no NOx, meanwhile NZVI-N was oxidized to Fe 2+. It is a relatively easy and cost-effective method for nitrate removal, so NZVI-N reducing nitrate has a great potential application in nitrate removal of groundwater. © 2012 Elsevier B.V.

The chemistry of acid catalyzed delignification of sugarcane bagasse in the ionic liquid trihexyl tetradecyl phosphonium chloride

This article reports on the cleavage of lignin ß-aryl ether bonds in sugarcane bagasse by the ionic liquid (IL) trihexyl tetradecyl phosphonium chloride [P66614] Cl, in the presence of catalytic amounts of mineral acid fca. 0.4%). The deligniflcation process of bagasse was studied over a range of temperatures (120°C to 150°C) by monitoring the production of ß-ketones (indicative of cleavage of ß-aryl ethers) using FTIR spectroscopy and by compositional analysis of the undissolved fractions. Maximum deligniflcation was obtained at 150°C, with 52% of lignin removed from the original lignin content of bagasse. No deligniflcation was observed in the absence of acid, which suggests that the reaction is acid catalyzed with the IL solubilizing the lignin fragments. The rate of deligniflcation was significantly higher at 150°C, suggesting that crossing the glass transition temperature of lignin effects greater freedom of rotation about the propanoid carbon-carbon bonds and leads to increased cleavage of ß-aryl ethers. An attempt has been made to propose a probable mechanism of deligniflcation of bagasse with the phosphonuim IL. © Taylor & Francis Group, LLC.

Eliciting metacognitive experiences and reflection in a year 11 chemistry classroom : an activity theory perspective

Concerns regarding students' learning and reasoning in chemistry classrooms are well documented. Students' reasoning in chemistry should be characterized by conscious consideration of chemical phenomenon from laboratory work at macroscopic, molecular/sub-micro and symbolic levels. Further, students should develop metacognition in relation to such ways of reasoning about chemistry phenomena. Classroom change eliciting metacognitive experiences and metacognitive reflection is necessary to shift entrenched views of teaching and learning in students. In this study, Activity Theory is used as the framework for intepreting changes to the rules/customs and tools of the activity systems of two different classes of students taught by the same teacher, Frances, who was teaching chemical equilibrium to those classes in consecutive years. An interpretive methodolgy involving multiple data sources was employed. Frances explicitly changed her pedagogy in the second year to direct students attention to increasingly consider chemical phenomena at the molecular/sub-micro level. Additonally, she asked students not to use the textbook until toward the end of the equilibrium unit and sought to engage them in using their prior knowledge of chemistry to understand their observations from experiments. Frances' changed pedagogy elicited metacognitive experiences and reflection in students and challenged them to reconsider their metacognitive beliefs about learning chemistry and how it might be achieved. While teacher change is essential for science education reform, students are not passive players in the change efforts and they need to be convinced of the viability of teacher pedagogical change in the context of their goals, intentions, and beliefs.

Amphiphilic silicone archtectures via anaerobic thiol - ene chemistry

Despite broad application, few silicone-based surfactants of known structure or, therefore, surfactancy have been prepared because of an absence of selective routes and instability of silicones to acid and base. Herein the synthesis of a library of explicit silicone-poly(ethylene glycol) (PEG) materials is reported. Pure silicone fragments were generated by the B(C(6)F(5))(3)-catalyzed condensation of alkoxysilanes and vinyl-functionalized hydrosilanes. The resulting pure products were coupled to thiol-terminated PEG materials using photogenerated radicals under anaerobic conditions.

Assessment of flood-related recharge to alluvial aquifers of an irrigated catchment following extended drought conditions using 3D visualisation and environmental tracers, Lockyer Valley, southeast Queensland, Australia.

The Lockyer Valley in southeast Queensland, Australia, hosts an economically significant alluvial aquifer system which has been impacted by prolonged drought conditions (~1997 to ~ 2009). Throughout this time, the system was under continued groundwater extraction, resulting in severe aquifer depletion. By 2008, much of the aquifer was at <30% of storage but some relief occurred with rains in early 2009. However, between December 2010 and January 2011, most of southeast Queensland experienced unprecedented flooding, which generated significant aquifer recharge. In order to understand the spatial and temporal controls of groundwater recharge in the alluvium, a detailed 3D lithological property model of gravels, sands and clays was developed using GOCAD software. The spatial distribution of recharge throughout the catchment was assessed using hydrograph data from about 400 groundwater observation wells screened at the base of the alluvium. Water levels from these bores were integrated into a catchment-wide 3D geological model using the 3D geological modelling software GOCAD; the model highlights the complexity of recharge mechanisms. To support this analysis, groundwater tracers (e.g. major and minor ions, stable isotopes, 3H and 14C) were used as independent verification. The use of these complementary methods has allowed the identification of zones where alluvial recharge primarily occurs from stream water during episodic flood events. However, the study also demonstrates that in some sections of the alluvium, rainfall recharge and discharge from the underlying basement into the alluvium are the primary recharge mechanisms of the alluvium. This is indicated by the absence of any response to the flood, as well as the observed old radiocarbon ages and distinct basement water chemistry signatures at these locations. Within the 3D geological model, integration of water chemistry and time-series displays of water level surfaces before and after the flood suggests that the spatial variations of the flood response in the alluvium are primarily controlled by the valley morphology and lithological variations within the alluvium. The integration of time-series of groundwater level surfaces in the 3D geological model also enables the quantification of the volumetric change of groundwater stored in the unconfined sections of this alluvial aquifer during drought and following flood events. The 3D representation and analysis of hydraulic and recharge information has considerable advantages over the traditional 2D approach. For example, while many studies focus on singular aspects of catchment dynamics and groundwater-surface water interactions, the 3D approach is capable of integrating multiple types of information (topography, geological, hydraulic, water chemistry and spatial) into a single representation which provides valuable insights into the major factors controlling aquifer processes.

Understanding hydrochemical processes using 3D models and hydrochemical facies in Wairau Plain groundwater, Marlborough

Three dimensional models and groundwater quality are combined to better understand and conceptualise groundwater systems in complex geological settings in the Wairau Plain, Marlborough. Hydrochemical facies, which are characteristic of distinct evolutionary pathways and a common hydrologic history of groundwaters, are identified within geological formations to assess natural water-rock interactions, redox potential and human agricultural impact on groundwater quality in the Wairau Plain.

Assessing the representativeness of a groundwater quality monitoring network

The monitoring sites comprising a state of the environment (SOE) network must be carefully selected to ensure that they will be representative of the broader resource. Hierarchical cluster analysis (HCA) is a data-driven technique that can potentially be employed to assess the representativeness of a SOE monitoring network. The objective of this paper is to explore the use of HCA as an approach for assessing the representativeness of the New Zealand National Groundwater Monitoring Programme (NGMP), which is comprised of 110 monitoring sites across the country.

Short answer versus multiple choice examination questions for first year chemistry

Multiple choice (MC) examinations are frequently used for the summative assessment of large classes because of their ease of marking and their perceived objectivity. However, traditional MC formats usually lead to a surface approach to learning, and do not allow students to demonstrate the depth of their knowledge or understanding. For these reasons, we have trialled the incorporation of short answer (SA) questions into the final examination of two first year chemistry units, alongside MC questions. Students’ overall marks were expected to improve, because they were able to obtain partial marks for the SA questions. Although large differences in some individual students’ performance in the two sections of their examinations were observed, most students received a similar percentage mark for their MC as for their SA sections and the overall mean scores were unchanged. In-depth analysis of all responses to a specific question, which was used previously as a MC question and in a subsequent semester in SA format, indicates that the SA format can have weaknesses due to marking inconsistencies that are absent for MC questions. However, inclusion of SA questions improved student scores on the MC section in one examination, indicating that their inclusion may lead to different study habits and deeper learning. We conclude that questions asked in SA format must be carefully chosen in order to optimise the use of marking resources, both financial and human, and questions asked in MC format should be very carefully checked by people trained in writing MC questions. These results, in conjunction with an analysis of the different examination formats used in first year chemistry units, have shaped a recommendation on how to reliably and cost-effectively assess first year chemistry, while encouraging higher order learning outcomes.