title: Passive in-situ estrogenic potency sampling with DGT-YES

authors: Iuele, Helena

abstract: The purpose of this research was to investigate the presence of bisphenolic plastics and synthetic estrogens in municipal water systems, as well as along the Waikato River. The concentration of these compounds was assessed using a novel combination of methods that allowed the actual levels of endocrine disruption to be ascertained. This was based on diffusive gradients in thin films (DGTs) coupled with high-performance liquid chromatography/mass spectrometry analysis (HPLC/MS) and the Yeast Estrogen Screen (YES).
DGT estimated time-integrated concentrations while HPLC/MS ensured a robust, automated and sensitive routine analysis. Most significantly, YES, a biomarker-based assay, was deployed to quantify the total estrogenic potency of the compounds adsorbed to the DGT matrix. The unique dimension of this research was to extend the application of DGTs to estrogen sampling and to combine the DGT and YES technique to provide in situ quantification of the estrogenic potency of water bodies through time.
DGTs were developed specifically for the sampling of BPA, BPAF, E2 and EE2. Several physical-chemical and chemical analyses were conducted to attest the suitability of the agarose (1.5%) and agarose (1.5%) – activated charcoal (1%) chosen respectively as diffusive gel and binding gel. They were found to be suitable for the detection of organic molecules with a bigger steric hindrance and agarose (1.5%) – AC (1%) appeared suitable for long deployments thanks to its high thermal resistance. An HPLC-MS method was optimised to quantify the compounds of interest. A methanol (MeOH, NH4OH 0.06 M)/water (H2O, NH4OH 0.06 M) fast gradient elution program of 15 min was chosen to elute the analytes, MS parameters were optimized for each compound and the negative mode was selected to perform the fragmentation. LODs and LOQs of all targets resulted in the nanomolar range assuming 24 h as deployment time at 25°C with a 0.54 mm thick diffusive gel. The sensitivity of the method was increased in the sub-nanomolar range by adopting long deployment times (18 days) thus enhancing the accumulation of the targets.The YES was successfully developed to quantify the total estrogenic potency of the DGTs eluted. The dose-response calibration curve of E2, employed as a control, demonstrated LOD and experimental EC50 values in the sub-nanomolar range. EE2, BPA and BPAF demonstrated agonistic endocrine activity, in particular EE2 being more potent than E2, while BPAF and BPA were less potent.
The environmental monitoring assessed the efficiency of removal of the selected ECs during the water treatment processes from river-to-tap and effluent-to-treated wastewater in Hamilton as well the water quality from source-to-outfall of the Waikato River. The HPLC-MS and YES results highlighted that primary treatments were not suitable for the removal of bisphenolic plastics and estrogens both at drinkable and wastewater treatment plants in Hamilton where they appear to worsen the water quality making these pollutants more available. At both treatment plants, the concentration and the estrogenic activity of the targets appeared to fluctuate around the same value, pointing out the inefficiency of removal of these compounds with the actual treatments. EE2 contributed the most to the estrogenic activity due to its higher concentration and higher potency at all sites.
The concentration and the estrogenic potency of all targets were found to be higher downstream at all sites monitored along the Waikato River. EE2 was the compound with the highest concentration at all sites. A moderate worsening of water quality was apparent moving from Taupo to Tuakau. The most polluted sites were Hamilton and Huntley after the outlets of wastewater treatment plants that serve the main conurbations in the area. The EDC concentrations recorded in November 2017 and February 2018 during the monitoring of the Waikato River at Hamilton upstream and downstream sites showed a significant dilution due to the weather conditions.
The data from a previous monitoring of the Waikato River adopting an SPE-HRGC/MS method were compared with those of the DGT-HPLC/MS investigation. The water quality appeared slightly worsened at all sites from 2013 to 2018 due to increased concentrations of BPA and EE2. The DGT-HPLC/MS quantification with the YES assay proved that not only active samplings but passive samplings as well can be coupled with a bioassay. This combined approach had the excellent potential to provide a reliable total estrogenic potency evaluation with time integrated concentrations. The use of the assay allowed estimation of the total estrogenic potency of the eluted DGT. The eluate appeared enriched by other compounds with estrogenic activity, suggesting this type of DGT could be suitable for the sampling and accumulation of other analytes that could be further investigated via HPLC/MS analysis. Compared to the traditional active approaches, DGT ensured sampling and concentration in one step, was easy to prepare and to use, required a very simple sample preparation step prior to analysis, and provided sensitivity in the sub-nanomolar range comparable to active sampling analyses. The YES assay was responsive, robust and easy to use compared to other assays that require laborious procedures and longer times for estrogenic potency evaluation and high sensitivity in the sub-nanomolar range comparable to other assays.

text: Passive in-situ estrogenic potency sampling with DGT-YES The purpose of this research was to investigate the presence of bisphenolic plastics and synthetic estrogens in municipal water systems, as well as along the Waikato River. The concentration of these compounds was assessed using a novel combination of methods that allowed the actual levels of endocrine disruption to be ascertained. This was based on diffusive gradients in thin films (DGTs) coupled with high-performance liquid chromatography/mass spectrometry analysis (HPLC/MS) and the Yeast Estrogen Screen (YES).
DGT estimated time-integrated concentrations while HPLC/MS ensured a robust, automated and sensitive routine analysis. Most significantly, YES, a biomarker-based assay, was deployed to quantify the total estrogenic potency of the compounds adsorbed to the DGT matrix. The unique dimension of this research was to extend the application of DGTs to estrogen sampling and to combine the DGT and YES technique to provide in situ quantification of the estrogenic potency of water bodies through time.
DGTs were developed specifically for the sampling of BPA, BPAF, E2 and EE2. Several physical-chemical and chemical analyses were conducted to attest the suitability of the agarose (1.5%) and agarose (1.5%) – activated charcoal (1%) chosen respectively as diffusive gel and binding gel. They were found to be suitable for the detection of organic molecules with a bigger steric hindrance and agarose (1.5%) – AC (1%) appeared suitable for long deployments thanks to its high thermal resistance. An HPLC-MS method was optimised to quantify the compounds of interest. A methanol (MeOH, NH4OH 0.06 M)/water (H2O, NH4OH 0.06 M) fast gradient elution program of 15 min was chosen to elute the analytes, MS parameters were optimized for each compound and the negative mode was selected to perform the fragmentation. LODs and LOQs of all targets resulted in the nanomolar range assuming 24 h as deployment time at 25°C with a 0.54 mm thick diffusive gel. The sensitivity of the method was increased in the sub-nanomolar range by adopting long deployment times (18 days) thus enhancing the accumulation of the targets.The YES was successfully developed to quantify the total estrogenic potency of the DGTs eluted. The dose-response calibration curve of E2, employed as a control, demonstrated LOD and experimental EC50 values in the sub-nanomolar range. EE2, BPA and BPAF demonstrated agonistic endocrine activity, in particular EE2 being more potent than E2, while BPAF and BPA were less potent.
The environmental monitoring assessed the efficiency of removal of the selected ECs during the water treatment processes from river-to-tap and effluent-to-treated wastewater in Hamilton as well the water quality from source-to-outfall of the Waikato River. The HPLC-MS and YES results highlighted that primary treatments were not suitable for the removal of bisphenolic plastics and estrogens both at drinkable and wastewater treatment plants in Hamilton where they appear to worsen the water quality making these pollutants more available. At both treatment plants, the concentration and the estrogenic activity of the targets appeared to fluctuate around the same value, pointing out the inefficiency of removal of these compounds with the actual treatments. EE2 contributed the most to the estrogenic activity due to its higher concentration and higher potency at all sites.
The concentration and the estrogenic potency of all targets were found to be higher downstream at all sites monitored along the Waikato River. EE2 was the compound with the highest concentration at all sites. A moderate worsening of water quality was apparent moving from Taupo to Tuakau. The most polluted sites were Hamilton and Huntley after the outlets of wastewater treatment plants that serve the main conurbations in the area. The EDC concentrations recorded in November 2017 and February 2018 during the monitoring of the Waikato River at Hamilton upstream and downstream sites showed a significant dilution due to the weather conditions.
The data from a previous monitoring of the Waikato River adopting an SPE-HRGC/MS method were compared with those of the DGT-HPLC/MS investigation. The water quality appeared slightly worsened at all sites from 2013 to 2018 due to increased concentrations of BPA and EE2. The DGT-HPLC/MS quantification with the YES assay proved that not only active samplings but passive samplings as well can be coupled with a bioassay. This combined approach had the excellent potential to provide a reliable total estrogenic potency evaluation with time integrated concentrations. The use of the assay allowed estimation of the total estrogenic potency of the eluted DGT. The eluate appeared enriched by other compounds with estrogenic activity, suggesting this type of DGT could be suitable for the sampling and accumulation of other analytes that could be further investigated via HPLC/MS analysis. Compared to the traditional active approaches, DGT ensured sampling and concentration in one step, was easy to prepare and to use, required a very simple sample preparation step prior to analysis, and provided sensitivity in the sub-nanomolar range comparable to active sampling analyses. The YES assay was responsive, robust and easy to use compared to other assays that require laborious procedures and longer times for estrogenic potency evaluation and high sensitivity in the sub-nanomolar range comparable to other assays.

year: 2019

title: Psychological collectivism and its effects on group member job performance and taking charge behaviour

authors: Belfield, William John

subjects: collectivism

abstract: The nature of work in contemporary organisations has become increasingly group orientated. Several studies have linked psychological collectivism with important outcomes for individuals working in groups. The present research sought to build upon existing research, via examining the performance benefits of psychological collectivism within the New Zealand context. This study had two main aims: to examine whether employees within New Zealand who are more collectivistic are better performing group members, and engage in increased taking charge behaviours; and to investigate the possible moderating role of TMX, or the quality of co-worker relationships, in these relationships. Participants in this study were employees from various businesses throughout New Zealand, representing a wide range of industries, who completed an online questionnaire. The questionnaire measured psychological collectivism, four dimensions of group member job performance (task performance, citizenship behaviour, counterproductive behaviour, and withdrawal behaviour), taking charge, and TMX-quality. To test the proposed hypotheses, correlation, regression, and moderation analyses were conducted in SPSS. Several of the proposed hypotheses received support: psychological collectivism positively predicted group member citizenship behaviour and taking charge behaviour, and negatively predicted group member counterproductive behaviour and group member withdrawal behaviour. TMX- quality significantly moderated the relationship between psychological collectivism and group member withdrawal behaviour. However, several of the proposed hypotheses did not receive support: psychological collectivism did not positively predict group member task performance, and TMX-quality did not significantly moderate the relationships between psychological collectivism and the other variables. Possible reasons why these hypotheses were unsupported are outlined. Additionally, significant non-hypothesized relationships were also obtained, which are discussed in detail. Concerning practical implications, organisations should aim to maximise psychological collectivism when necessary, via selection and placement or employee training and development programs. Moreover organisations should focus on improving the quality of co-worker relationships (i.e., TMX-quality). With respect to future research, research is needed which explicitly examines whether psychological collectivism can be developed in individuals. Taken together, the findings from this study highlight the far-reaching performance benefits of psychological collectivism and high-quality TMX in the workplace.

text: Psychological collectivism and its effects on group member job performance and taking charge behaviour The nature of work in contemporary organisations has become increasingly group orientated. Several studies have linked psychological collectivism with important outcomes for individuals working in groups. The present research sought to build upon existing research, via examining the performance benefits of psychological collectivism within the New Zealand context. This study had two main aims: to examine whether employees within New Zealand who are more collectivistic are better performing group members, and engage in increased taking charge behaviours; and to investigate the possible moderating role of TMX, or the quality of co-worker relationships, in these relationships. Participants in this study were employees from various businesses throughout New Zealand, representing a wide range of industries, who completed an online questionnaire. The questionnaire measured psychological collectivism, four dimensions of group member job performance (task performance, citizenship behaviour, counterproductive behaviour, and withdrawal behaviour), taking charge, and TMX-quality. To test the proposed hypotheses, correlation, regression, and moderation analyses were conducted in SPSS. Several of the proposed hypotheses received support: psychological collectivism positively predicted group member citizenship behaviour and taking charge behaviour, and negatively predicted group member counterproductive behaviour and group member withdrawal behaviour. TMX- quality significantly moderated the relationship between psychological collectivism and group member withdrawal behaviour. However, several of the proposed hypotheses did not receive support: psychological collectivism did not positively predict group member task performance, and TMX-quality did not significantly moderate the relationships between psychological collectivism and the other variables. Possible reasons why these hypotheses were unsupported are outlined. Additionally, significant non-hypothesized relationships were also obtained, which are discussed in detail. Concerning practical implications, organisations should aim to maximise psychological collectivism when necessary, via selection and placement or employee training and development programs. Moreover organisations should focus on improving the quality of co-worker relationships (i.e., TMX-quality). With respect to future research, research is needed which explicitly examines whether psychological collectivism can be developed in individuals. Taken together, the findings from this study highlight the far-reaching performance benefits of psychological collectivism and high-quality TMX in the workplace.

year: 2019

title: Place attachment of Ngāi Te Ahi to Hairini Marae

authors: Teddy, Lani

subjects: Hairini

abstract: Twelve members of Ngāi Te Ahi, a hapū from Tauranga, were interviewed to explore how they talk about their place attachment to Hairini Marae.  This was organized around five key dimensions of place attachment taken from the literature—continuity, distinctiveness, symbolism, attachment and familiarity.  We found that in discussing all dimensions, place attachment was equally about social and cultural relationships, history, and socialization.  Place attachment for groups such as Māori is complex because it encompasses all social relationships past and present.  The implication for those working with Māori is to take seriously the wider connotations of place when talking to Māori about marae, traditional homelands, and their land.

text: Place attachment of Ngāi Te Ahi to Hairini Marae Twelve members of Ngāi Te Ahi, a hapū from Tauranga, were interviewed to explore how they talk about their place attachment to Hairini Marae.  This was organized around five key dimensions of place attachment taken from the literature—continuity, distinctiveness, symbolism, attachment and familiarity.  We found that in discussing all dimensions, place attachment was equally about social and cultural relationships, history, and socialization.  Place attachment for groups such as Māori is complex because it encompasses all social relationships past and present.  The implication for those working with Māori is to take seriously the wider connotations of place when talking to Māori about marae, traditional homelands, and their land.

year: 2008