title: Extractable organics and colour in a bleached kraft mill effluent land application system and recipient ground waters

authors: Mills, Geoffrey Newton

abstract: This thesis describes a study of the behaviour of extractable organics and colour in a land application system used to treat highly coloured, organic-rich, alkali extraction stage and foul condensate effluents from a traditional bleached kraft mill. The land application system comprised 44 unlined seepage basins, totalling 86 ha in area, into which approximately 10,000 m³ d⁻¹ effluent was loaded for approximately eight months of each year. The study aimed to determine (1) the effectiveness of the system for treating major effluent organics, including monoterpenes, fatty acids, resin acids, chlorophenolics, and colour, and (2) the effects of the system on organic contamination of sediments, aquifer materials, and ground waters. 

The study was carried out in four parts, investigating: (i) the behaviour of extractable organics and colour in the effluent drains and seepage basins; (ii) the penetration of extractable organics into the sediments beneath the seepage basins; (iii) the organic chemistry of shallow ground waters beneath the seepage system, and of deeper off-site ground waters; and (iv) behaviour of extractable organics and colour in laboratory soil-column simulating the land application process. In addition, a review of land application of pulp mill effluents was carried out, and analytical methods for determining extractable organics in effluents, sediments, and ground waters were developed.

Concentrations of extractable organics and chlorophenolics were reduced by >95% over a 40 day period in the seepage basins. Removal rates decreased in the order fatty acids > chlorophenolics ≈ monoterpenes > resin acids. Resin acids underwent reductive and oxidative transformations, producing transient intermediates including 13-abietenoic acid and 13β-hydroxyabietanoic acid. A suite of relatively stable transformed species, dominated by the saturated compound abietanoic acid, remained in the seepage pond after 40 days. Colour removal over the same period was approximately 25%.

High concentrations of effluent-derived extractable organics were found in surficial sediments beneath the seepage basins. Major compounds were resin acids, largely saturated species, and diterpene hydrocarbon transformation products. Diterpene hydrocarbons were dominated by retene, fichtelite, and dehydroabietin. Surficial sediments contained concentrations of total resin acids and diterpene hydrocarbons of up to 10,000 mg kg⁻¹. Concentrations dropped with depth, but high levels were found in discrete zones at depths of up to 5 m beneath the surface. This indicated that effluent movement was occurring through permeable conduits rather than via uniform infiltration through the soil, and was consistent with the fractured geology of the site. 

Ground waters taken from seven well clusters, sampling depths between 2 and 15 m beneath the seepage basins, contained elevated sodium and chloride concentrations (200-400 mg L⁻¹) and spatially variable colour levels (100-2000 CPU). Effluent-derived extractable organics were also found in variable concentrations. Major compounds were methyl-substituted 2-cyclopentenones, resin acids, and diterpene hydrocarbons. Resin acids and diterpene hydrocarbons were the generally dominant compound classes, concentrations totalling 20-2600 μg L⁻¹. Preliminary assessment of chlorophenolics found low levels, totalling 2-4 μg L⁻¹ in the most contaminated ground waters. The results indicated that contamination of shallow ground water was occurring, but the nature and level of this contamination was highly spatially variable. As found for the sediment studies, these findings were consistent with effluent infiltration through heterogeneous, fractured, sub-surface geology.

The hydrogeology of the area was determined to be dominated by ground water movement through fractured zones in four major ignimbrite aquifers. Wells were placed at depths between 9 and 110 m, and at distances from immediately adjacent to 2.7 km from the seepage area to sample ground water from these zones. Contamination was found largely within the highly fractured, high flow zones of two of these units, the Marshall A and, to a lesser extent, the Marshall B ignimbrite aquifers. Concentrations of effluent-sourced extractable organics (largely resin acids and diterpene hydrocarbons) and colour were highest immediately beneath the seepage area, maximum concentrations of 110 μg L⁻¹ total resin acids and diterpene hydrocarbons, and 900 CPU colour being found. Concentrations dropped rapidly with distance
from the ponds, decreasing by approximately 90% within about 100 m from the seepage area. There was evidence for retardation of organics relative to sodium and chloride in the off-site aquifers.

Laboratory simulations of effluent infiltration through seepage site soils were carried out under two application regimes (permanently flooded, and flood-dry cycle) to determine the range of treatment possibilities occurring in the seepage system. Leachate chemistry was monitored over an approximately two year period, and soil extractives measured at the end of the study. Mass balance was used to estimate effluent treatment efficiency. The flood-dry (aerobic) application regime resulted in essentially compete degradative removal of extractable organics. 

Under the flooded (anaerobic) regime, extractable organic removal was limited for all constituents other than fatty acids, which were >90% removed. Resin acids were strongly retained by the soil, approximately 72% remaining in the soil at the end of the study. Approximately 25% was recovered in the leachate. Monoterpenes were highly mobile, moving rapidly through the soil. A relatively stable suite of transformed compounds was found in the leachates. Monoterpene removal was estimated to be approximately 55%. Under flooded conditions, transformation rather than degradative removal of extractable organics occurred. 

Colour intensification, rather than reduction, occurred at times in both application regimes. At the end of the study, colour removal in the flood-dry cycle regime was 2%, and in the flooded regime an increase of 51% was measured.

In summary, the study found that the land application system resulted in large decreases (>95%) in the concentrations of extractable organics, but little overall treatment of effluent colour. Ground waters affected by effluent infiltration were highly variable in composition, but in general contained elevated colour levels, and moderate-to-low concentrations of extractable organics. Resin acids and diterpene hydrocarbons were the dominant class of extractable organics found in sediments and ground waters beneath the seepage system.

text: Extractable organics and colour in a bleached kraft mill effluent land application system and recipient ground waters This thesis describes a study of the behaviour of extractable organics and colour in a land application system used to treat highly coloured, organic-rich, alkali extraction stage and foul condensate effluents from a traditional bleached kraft mill. The land application system comprised 44 unlined seepage basins, totalling 86 ha in area, into which approximately 10,000 m³ d⁻¹ effluent was loaded for approximately eight months of each year. The study aimed to determine (1) the effectiveness of the system for treating major effluent organics, including monoterpenes, fatty acids, resin acids, chlorophenolics, and colour, and (2) the effects of the system on organic contamination of sediments, aquifer materials, and ground waters. 

The study was carried out in four parts, investigating: (i) the behaviour of extractable organics and colour in the effluent drains and seepage basins; (ii) the penetration of extractable organics into the sediments beneath the seepage basins; (iii) the organic chemistry of shallow ground waters beneath the seepage system, and of deeper off-site ground waters; and (iv) behaviour of extractable organics and colour in laboratory soil-column simulating the land application process. In addition, a review of land application of pulp mill effluents was carried out, and analytical methods for determining extractable organics in effluents, sediments, and ground waters were developed.

Concentrations of extractable organics and chlorophenolics were reduced by >95% over a 40 day period in the seepage basins. Removal rates decreased in the order fatty acids > chlorophenolics ≈ monoterpenes > resin acids. Resin acids underwent reductive and oxidative transformations, producing transient intermediates including 13-abietenoic acid and 13β-hydroxyabietanoic acid. A suite of relatively stable transformed species, dominated by the saturated compound abietanoic acid, remained in the seepage pond after 40 days. Colour removal over the same period was approximately 25%.

High concentrations of effluent-derived extractable organics were found in surficial sediments beneath the seepage basins. Major compounds were resin acids, largely saturated species, and diterpene hydrocarbon transformation products. Diterpene hydrocarbons were dominated by retene, fichtelite, and dehydroabietin. Surficial sediments contained concentrations of total resin acids and diterpene hydrocarbons of up to 10,000 mg kg⁻¹. Concentrations dropped with depth, but high levels were found in discrete zones at depths of up to 5 m beneath the surface. This indicated that effluent movement was occurring through permeable conduits rather than via uniform infiltration through the soil, and was consistent with the fractured geology of the site. 

Ground waters taken from seven well clusters, sampling depths between 2 and 15 m beneath the seepage basins, contained elevated sodium and chloride concentrations (200-400 mg L⁻¹) and spatially variable colour levels (100-2000 CPU). Effluent-derived extractable organics were also found in variable concentrations. Major compounds were methyl-substituted 2-cyclopentenones, resin acids, and diterpene hydrocarbons. Resin acids and diterpene hydrocarbons were the generally dominant compound classes, concentrations totalling 20-2600 μg L⁻¹. Preliminary assessment of chlorophenolics found low levels, totalling 2-4 μg L⁻¹ in the most contaminated ground waters. The results indicated that contamination of shallow ground water was occurring, but the nature and level of this contamination was highly spatially variable. As found for the sediment studies, these findings were consistent with effluent infiltration through heterogeneous, fractured, sub-surface geology.

The hydrogeology of the area was determined to be dominated by ground water movement through fractured zones in four major ignimbrite aquifers. Wells were placed at depths between 9 and 110 m, and at distances from immediately adjacent to 2.7 km from the seepage area to sample ground water from these zones. Contamination was found largely within the highly fractured, high flow zones of two of these units, the Marshall A and, to a lesser extent, the Marshall B ignimbrite aquifers. Concentrations of effluent-sourced extractable organics (largely resin acids and diterpene hydrocarbons) and colour were highest immediately beneath the seepage area, maximum concentrations of 110 μg L⁻¹ total resin acids and diterpene hydrocarbons, and 900 CPU colour being found. Concentrations dropped rapidly with distance
from the ponds, decreasing by approximately 90% within about 100 m from the seepage area. There was evidence for retardation of organics relative to sodium and chloride in the off-site aquifers.

Laboratory simulations of effluent infiltration through seepage site soils were carried out under two application regimes (permanently flooded, and flood-dry cycle) to determine the range of treatment possibilities occurring in the seepage system. Leachate chemistry was monitored over an approximately two year period, and soil extractives measured at the end of the study. Mass balance was used to estimate effluent treatment efficiency. The flood-dry (aerobic) application regime resulted in essentially compete degradative removal of extractable organics. 

Under the flooded (anaerobic) regime, extractable organic removal was limited for all constituents other than fatty acids, which were >90% removed. Resin acids were strongly retained by the soil, approximately 72% remaining in the soil at the end of the study. Approximately 25% was recovered in the leachate. Monoterpenes were highly mobile, moving rapidly through the soil. A relatively stable suite of transformed compounds was found in the leachates. Monoterpene removal was estimated to be approximately 55%. Under flooded conditions, transformation rather than degradative removal of extractable organics occurred. 

Colour intensification, rather than reduction, occurred at times in both application regimes. At the end of the study, colour removal in the flood-dry cycle regime was 2%, and in the flooded regime an increase of 51% was measured.

In summary, the study found that the land application system resulted in large decreases (>95%) in the concentrations of extractable organics, but little overall treatment of effluent colour. Ground waters affected by effluent infiltration were highly variable in composition, but in general contained elevated colour levels, and moderate-to-low concentrations of extractable organics. Resin acids and diterpene hydrocarbons were the dominant class of extractable organics found in sediments and ground waters beneath the seepage system.

year: 1997

title: Cooperative education: Integrating classroom and workplace learning

authors: Eames, Chris W.

subjects: cooperative education

abstract: Cooperative education (co-op) is a strategy of education that combines academic learning in the classroom with real-world practice in a relevant workplace. To provide this mix of learning opportunities, co-op involves collaboration among students, educational institutions, and employers. Real-world experience for students in the form of work-based placements or internships can serve to provide entry for learners into a particular community of practice. Theorising and research into student learning through cooperative education has focussed on the experiential nature of the learning opportunity, and more latterly through sociocultural views of learning. These latter views help us to understand that cooperative education exposes students to worlds of learning that are different but complementary. These complementary worlds have different sociocultural dimensions that afford different learning opportunities to students. Clearly defined integrative pathways are required that allow students to make sense of the learning that they are afforded. The real strength of cooperative education as a strategy of practice-based learning is not that students gain opportunities to learn in the classroom and in the workplace, but that these opportunities are integrated to create learning that is more than the sum of the two parts.

text: Cooperative education: Integrating classroom and workplace learning Cooperative education (co-op) is a strategy of education that combines academic learning in the classroom with real-world practice in a relevant workplace. To provide this mix of learning opportunities, co-op involves collaboration among students, educational institutions, and employers. Real-world experience for students in the form of work-based placements or internships can serve to provide entry for learners into a particular community of practice. Theorising and research into student learning through cooperative education has focussed on the experiential nature of the learning opportunity, and more latterly through sociocultural views of learning. These latter views help us to understand that cooperative education exposes students to worlds of learning that are different but complementary. These complementary worlds have different sociocultural dimensions that afford different learning opportunities to students. Clearly defined integrative pathways are required that allow students to make sense of the learning that they are afforded. The real strength of cooperative education as a strategy of practice-based learning is not that students gain opportunities to learn in the classroom and in the workplace, but that these opportunities are integrated to create learning that is more than the sum of the two parts.

year: 2010

title: Homai raa. Kia purutia, kia hereherea, taawhiwhi taamau. Ka pai. Taawhiwhi  taumau, he tauira waiora a Waikato : The creation of a Waikato-specific Maaori health model

authors: Haggie, Marrin Brian Pikitawhaki

subjects: Taawhiwhi Taamau

abstract: This Doctoral rangahau (research) sought to create a Maaori (Indigenous people of New Zealand) health model specific to the health needs and desires of the people of Waikato (The collective name of the tribes of the Waikato basin). Globally, minority populations (including Maaori) are consistently and disproportionately over represented in many health, education and incarceration statistics. Colonisation, oppression and racial prejudices have been identified as the root causes for the statistical imbalances prevalent in society. Indigenous populations have endured suffering caused by disconnection from heritage, traditional practices, ancestral beliefs and the natural environment. All are consequences of legislative enforcement and an oppressive, colonialist attitude that patronises indigenous populations (i.e., that assumes the coloniser knows what is best for the colonised). 

For the majority of colonisation, the health models and frameworks intended to benefit indigenous peoples, yet designed and implemented by colonial based, oppressive governments and by institutions rooted in colonialist ideals, have consistently failed to provide and deliver health and wellness for indigenous peoples. The fact that indigenous peoples’ health continues to be poorer than their non-indigenous counterparts, in the majority of health measures, suggests models and frameworks designed by non-indigenous people do not work for indigenous populations. This has led to an emergence of indigenous and minority populations’ movements seeking to emancipate themselves from the shackles of colonial oppression. 

Pioneering health models and frameworks designed to counter the failures of those designed by the oppressor have provided salvation for indigenous peoples and have allowed the voices of minority populations to be heard in the health and wellbeing context; however the majority of these models have been overly generic. Yet, they have provided foundations that now must be built upon to enable a focus on what specific populations require to ensure their health and lifestyle ideals are supported and strengthened.

As whaanau (family), marae (place of gathering and belonging for interrelated families), hapuu (subtribe), and as an iwi (tribe), Waikato have a responsibility to our taiao (natural environment), ourselves and to future generations to ensure the health of Waikato and that Waikatotanga (Waikato culture and practice) continues to grow, prosper, and flourish. Therefore, as a polity we must assert the control and direction of our iwi by determining and creating our own models and frameworks to ensure the survival, the growth, and the success of our people.

This Rangahau Kaupapa Waikato (Waikato focused research) is centered on the question ‘What elements must be considered in the creation and the application of a Waikato-specific, Maaori health model?’ Contemporary literature and research regarding health and the impacts on Indigenous and Maaori health specifically, was used to review the successes and failures of contemporary health models. 

Supported and framed by a Rangahau Kaupapa Maaori (Maaori focused research) approach, this Rangahau Kaupapa Waikato utilised Waikato koorero (stories), beliefs, practices and methodologies, interspersed with Qualitative Methodology and Thematic Analysis. Fourteen semi-structured interviews with tribal leaders and holders of tribal knowledge, referred to as taniwha, were conducted. Each taniwha shared their knowledge, understandings, and experiences to inform and contribute to the creation of a holistic health model specific to the iwi of Waikato.

The findings illustrate continued connection to the Waikato awa (river), the taiao (natural environment), wairuatanga (spirituality), ancestral knowledge and practices, the Kiingitanga (Maaori King Movement) and to the iwi itself are critical to the perpetuation of the waiora (health) of the Waikato iwi and of Waikatotanga in its multiple forms.

The model created as the primary outcome of this research, The Taawhiwhi Taamau Model of Waiora (Taawhiwhi Taamau), was designed to act as a vehicle which seeks to enable individual iwi members, and the polities that they belong, to achieve Mana-motuhake (autonomy) and self-determination of their own health. Taawhiwhi Taamau seeks to inform its adopters that Mana-motuhake can be achieved without having to compromise any of the tikanga (protocol) and kawa (custom) of our iwi and of our ancestors in favour of colonial government introduced, western ideals. Thereby removing the oppressor from the implementation and application of health. 

Taawhiwhi Taamau is a health model entrenched in Waikatotanga that utilises the beliefs and practices of our ancestors, and subsequently, our iwi to facilitate Tupuna (ancestor) Guided Living. The model encourages the individual iwi member to build solid foundations of waiora, seek knowledge and understanding of our tupuna, and use the experiences in life to act as taniwha for others seeking guidance, knowledge, connection, understanding and waiora. 

The adoption and practice of Taawhiwhi Taamau suggests individuals will find a new, refreshed connection to tupuna, maatauranga (wisdom, knowledge), wairuatanga and Waikatotanga, therefore, increasing waiora. Increased waiora of the individual increases the waiora and the capacity of one’s whaanau, marae and hapuu thereby increasing the waiora and the capacity of the iwi. Increased waiora and capacity of the iwi increases the likelihood of Waikatotanga, maatauranga, wairuatanga and, thus, the perpetuation of Tupuna Guided Living. Consequently, encapsulating the essence of Taawhiwhi Taamau as a model and as the lesson learned in the Pai Maarire Te Kura o te Ahiahi, ‘Homai ra, kia purutia, kia hereherea, taawhiwhi taamau. Ka Pai’.

text: Homai raa. Kia purutia, kia hereherea, taawhiwhi taamau. Ka pai. Taawhiwhi  taumau, he tauira waiora a Waikato : The creation of a Waikato-specific Maaori health model This Doctoral rangahau (research) sought to create a Maaori (Indigenous people of New Zealand) health model specific to the health needs and desires of the people of Waikato (The collective name of the tribes of the Waikato basin). Globally, minority populations (including Maaori) are consistently and disproportionately over represented in many health, education and incarceration statistics. Colonisation, oppression and racial prejudices have been identified as the root causes for the statistical imbalances prevalent in society. Indigenous populations have endured suffering caused by disconnection from heritage, traditional practices, ancestral beliefs and the natural environment. All are consequences of legislative enforcement and an oppressive, colonialist attitude that patronises indigenous populations (i.e., that assumes the coloniser knows what is best for the colonised). 

For the majority of colonisation, the health models and frameworks intended to benefit indigenous peoples, yet designed and implemented by colonial based, oppressive governments and by institutions rooted in colonialist ideals, have consistently failed to provide and deliver health and wellness for indigenous peoples. The fact that indigenous peoples’ health continues to be poorer than their non-indigenous counterparts, in the majority of health measures, suggests models and frameworks designed by non-indigenous people do not work for indigenous populations. This has led to an emergence of indigenous and minority populations’ movements seeking to emancipate themselves from the shackles of colonial oppression. 

Pioneering health models and frameworks designed to counter the failures of those designed by the oppressor have provided salvation for indigenous peoples and have allowed the voices of minority populations to be heard in the health and wellbeing context; however the majority of these models have been overly generic. Yet, they have provided foundations that now must be built upon to enable a focus on what specific populations require to ensure their health and lifestyle ideals are supported and strengthened.

As whaanau (family), marae (place of gathering and belonging for interrelated families), hapuu (subtribe), and as an iwi (tribe), Waikato have a responsibility to our taiao (natural environment), ourselves and to future generations to ensure the health of Waikato and that Waikatotanga (Waikato culture and practice) continues to grow, prosper, and flourish. Therefore, as a polity we must assert the control and direction of our iwi by determining and creating our own models and frameworks to ensure the survival, the growth, and the success of our people.

This Rangahau Kaupapa Waikato (Waikato focused research) is centered on the question ‘What elements must be considered in the creation and the application of a Waikato-specific, Maaori health model?’ Contemporary literature and research regarding health and the impacts on Indigenous and Maaori health specifically, was used to review the successes and failures of contemporary health models. 

Supported and framed by a Rangahau Kaupapa Maaori (Maaori focused research) approach, this Rangahau Kaupapa Waikato utilised Waikato koorero (stories), beliefs, practices and methodologies, interspersed with Qualitative Methodology and Thematic Analysis. Fourteen semi-structured interviews with tribal leaders and holders of tribal knowledge, referred to as taniwha, were conducted. Each taniwha shared their knowledge, understandings, and experiences to inform and contribute to the creation of a holistic health model specific to the iwi of Waikato.

The findings illustrate continued connection to the Waikato awa (river), the taiao (natural environment), wairuatanga (spirituality), ancestral knowledge and practices, the Kiingitanga (Maaori King Movement) and to the iwi itself are critical to the perpetuation of the waiora (health) of the Waikato iwi and of Waikatotanga in its multiple forms.

The model created as the primary outcome of this research, The Taawhiwhi Taamau Model of Waiora (Taawhiwhi Taamau), was designed to act as a vehicle which seeks to enable individual iwi members, and the polities that they belong, to achieve Mana-motuhake (autonomy) and self-determination of their own health. Taawhiwhi Taamau seeks to inform its adopters that Mana-motuhake can be achieved without having to compromise any of the tikanga (protocol) and kawa (custom) of our iwi and of our ancestors in favour of colonial government introduced, western ideals. Thereby removing the oppressor from the implementation and application of health. 

Taawhiwhi Taamau is a health model entrenched in Waikatotanga that utilises the beliefs and practices of our ancestors, and subsequently, our iwi to facilitate Tupuna (ancestor) Guided Living. The model encourages the individual iwi member to build solid foundations of waiora, seek knowledge and understanding of our tupuna, and use the experiences in life to act as taniwha for others seeking guidance, knowledge, connection, understanding and waiora. 

The adoption and practice of Taawhiwhi Taamau suggests individuals will find a new, refreshed connection to tupuna, maatauranga (wisdom, knowledge), wairuatanga and Waikatotanga, therefore, increasing waiora. Increased waiora of the individual increases the waiora and the capacity of one’s whaanau, marae and hapuu thereby increasing the waiora and the capacity of the iwi. Increased waiora and capacity of the iwi increases the likelihood of Waikatotanga, maatauranga, wairuatanga and, thus, the perpetuation of Tupuna Guided Living. Consequently, encapsulating the essence of Taawhiwhi Taamau as a model and as the lesson learned in the Pai Maarire Te Kura o te Ahiahi, ‘Homai ra, kia purutia, kia hereherea, taawhiwhi taamau. Ka Pai’.

year: 2021