title: Rates, controls and potential adverse effects of nitrate removal in a denitrification bed

authors: Warneke, Sören

subjects: denitrification

abstract: Denitrification beds are a simple approach for removing nitrate (NO₃⁻) from a range of point sources prior to discharge into receiving waters. These beds are large containers filled with woodchips that act as an energy source for microorganisms to convert NO₃⁻ to nitrogen (N) gases (N₂O, N₂) through denitrification. This study investigated the biological mechanism of NO₃⁻ removal, its controlling factors and its adverse effects in a large denitrification bed (176 m × 5 m × 1.5 m) receiving effluent with a high NO₃⁻ concentration (>100 g N m⁻³) from a hydroponic glasshouse (Karaka, Auckland, New Zealand). Samples of woodchips and water were collected from 12 sites along the bed every two months for one year, along with measurements of gas fluxes from the bed surface. Denitrifying enzyme activity (DEA), factors limiting denitrification (availability of carbon, dissolved organic carbon (DOC), dissolved oxygen (DO), temperature, pH, and concentrations of NO₃⁻, nitrite (NO₂⁻) and sulfide (S²⁻)), greenhouse gas (GHG) production – as nitrous oxide (N₂O), methane (CH₄), carbon dioxide (CO₂) – and carbon (C) loss were determined. NO₃⁻-N concentration declined along the bed with total NO₃⁻-N removal rates of 10.1 kg N d⁻¹ for the whole bed or 7.6 g N m⁻³ d⁻¹. NO₃⁻-N removal rates increased with temperature (Q₁₀ = 2.0). In laboratory incubations, denitrification was always limited by C availability rather than by NO₃⁻. DO levels were above 0.5 mg L⁻¹ at the inlet but did not limit NO₃⁻-N removal. pH increased steadily from about 6 to 7 along the length of the bed. Dissolved inorganic carbon (C-CO₂) increased in average about 27.8 mg L⁻¹, whereas DOC decreased slightly by about 0.2 mg L⁻¹ along the length of the bed. The bed surface emitted on average 78.58 μg m−² min⁻¹ N₂O-N (reflecting 1% of the removed NO₃⁻-N), 0.238 μg m⁻² min⁻¹ CH₄ and 12.6 mg m⁻² min⁻¹ CO₂. Dissolved N₂O-N increased along the length of the bed and the bed released on average 362 g dissolved N₂O-N per day coupled with N₂O emission at the surface about 4.3% of the removed NO₃⁻-N as N₂O. Mechanisms to reduce the production of this GHG need to be investigated if denitrification beds are commonly used. Dissolved CH₄ concentrations showed no trends along the length of the bed, ranging from 5.28 μg L⁻¹ to 34.24 μg L⁻¹. Sulfate (SO₄²⁻) concentrations declined along the length of the bed on three of six samplings; however, declines in SO₄²⁻ did not appear to be due to SO₄²⁻ reduction because S²⁻ concentrations were generally undetectable. Ammonium (NH₄⁺) (range: <0.0007 mg L⁻¹ to 2.12 mg L⁻¹) and NO₂⁻ concentrations (range: 0.0018 mg L⁻¹ to 0.95 mg L⁻¹) were always very low suggesting that anammox was an unlikely mechanism for NO₃⁻ removal in the bed. C longevity was calculated from surface emission rates of CO₂ and release of dissolved carbon (DC) and suggested that there would be ample C available to support denitrification for up to 39 years.
This study showed that denitrification beds can be an efficient tool for reducing high NO₃⁻ concentrations in effluents but did produce some GHGs. Over the course of a year NO₃⁻ removal rates were always limited by C and temperature and not by NO₃⁻ or DO concentration.

text: Rates, controls and potential adverse effects of nitrate removal in a denitrification bed Denitrification beds are a simple approach for removing nitrate (NO₃⁻) from a range of point sources prior to discharge into receiving waters. These beds are large containers filled with woodchips that act as an energy source for microorganisms to convert NO₃⁻ to nitrogen (N) gases (N₂O, N₂) through denitrification. This study investigated the biological mechanism of NO₃⁻ removal, its controlling factors and its adverse effects in a large denitrification bed (176 m × 5 m × 1.5 m) receiving effluent with a high NO₃⁻ concentration (>100 g N m⁻³) from a hydroponic glasshouse (Karaka, Auckland, New Zealand). Samples of woodchips and water were collected from 12 sites along the bed every two months for one year, along with measurements of gas fluxes from the bed surface. Denitrifying enzyme activity (DEA), factors limiting denitrification (availability of carbon, dissolved organic carbon (DOC), dissolved oxygen (DO), temperature, pH, and concentrations of NO₃⁻, nitrite (NO₂⁻) and sulfide (S²⁻)), greenhouse gas (GHG) production – as nitrous oxide (N₂O), methane (CH₄), carbon dioxide (CO₂) – and carbon (C) loss were determined. NO₃⁻-N concentration declined along the bed with total NO₃⁻-N removal rates of 10.1 kg N d⁻¹ for the whole bed or 7.6 g N m⁻³ d⁻¹. NO₃⁻-N removal rates increased with temperature (Q₁₀ = 2.0). In laboratory incubations, denitrification was always limited by C availability rather than by NO₃⁻. DO levels were above 0.5 mg L⁻¹ at the inlet but did not limit NO₃⁻-N removal. pH increased steadily from about 6 to 7 along the length of the bed. Dissolved inorganic carbon (C-CO₂) increased in average about 27.8 mg L⁻¹, whereas DOC decreased slightly by about 0.2 mg L⁻¹ along the length of the bed. The bed surface emitted on average 78.58 μg m−² min⁻¹ N₂O-N (reflecting 1% of the removed NO₃⁻-N), 0.238 μg m⁻² min⁻¹ CH₄ and 12.6 mg m⁻² min⁻¹ CO₂. Dissolved N₂O-N increased along the length of the bed and the bed released on average 362 g dissolved N₂O-N per day coupled with N₂O emission at the surface about 4.3% of the removed NO₃⁻-N as N₂O. Mechanisms to reduce the production of this GHG need to be investigated if denitrification beds are commonly used. Dissolved CH₄ concentrations showed no trends along the length of the bed, ranging from 5.28 μg L⁻¹ to 34.24 μg L⁻¹. Sulfate (SO₄²⁻) concentrations declined along the length of the bed on three of six samplings; however, declines in SO₄²⁻ did not appear to be due to SO₄²⁻ reduction because S²⁻ concentrations were generally undetectable. Ammonium (NH₄⁺) (range: <0.0007 mg L⁻¹ to 2.12 mg L⁻¹) and NO₂⁻ concentrations (range: 0.0018 mg L⁻¹ to 0.95 mg L⁻¹) were always very low suggesting that anammox was an unlikely mechanism for NO₃⁻ removal in the bed. C longevity was calculated from surface emission rates of CO₂ and release of dissolved carbon (DC) and suggested that there would be ample C available to support denitrification for up to 39 years.
This study showed that denitrification beds can be an efficient tool for reducing high NO₃⁻ concentrations in effluents but did produce some GHGs. Over the course of a year NO₃⁻ removal rates were always limited by C and temperature and not by NO₃⁻ or DO concentration.

year: 2011

title: Sedimentation And Hydrodynamics of Whitianga Estuary

authors: Reeve, Glen M.D

subjects: Hydrodynamics

abstract: Whitianga Estuary is a bayhead barrier type estuary located on the east of the Coromandel Peninsula, North Island, New Zealand. The catchment has undergone many land-use changes since pre-European settlement. In some areas of the catchment land-use has changed from native forest to grasslands to forestry and back to pasture. These changes in catchment land-use all contribute to increased sedimentation into the estuary. Development of the estuary itself has also occurred in recent times. Much growth has been focussed around the estuary due to Whitianga town-ship having a large boating community, and includes a 170 berth marina and wharf situated at
the tidal inlet entrance to the estuary. These, and the extensive canal development engineering works can have substantial impacts on the
sedimentation regime, and may modify tidal circulation, flushing, and sediment deposition within the estuary.

The principle aim of this research is to assess hydrodynamics and sedimentation of the estuary for future management and development purposes, and also to model different scenarios in order to determine the most cost effective, and least obtrusive design for a proposed boat-ramp and
approach channel near the marina.

To determine sedimentation rates, sediment cores from four locations were collected to depths of 1 m. Coring locations were chosen based on
preliminary model run results, selecting areas that appeared to be long-term sediment sinks of a stable nature. Cores were divided into 10 mm sections and prepared for 210Pb dating and heavy metal analysis, to make an assessment of the vertical sedimentation rates. Recent sedimentation rates were found to be as high as 9 mm/yr post-1950s and past sedimentation rates
as high as 30 mm/yr pre-1950s. The use of heavy metal analysis for dating proved difficult as the background levels of the conservative elements used to normalise results varied, making the geochemical analysis approach inappropriate.

As bathymetry is one of the most important aspects of modelling, a large amount of surveying was undertaken for this study. LiDAR, singlebeam data, and recent rectified aerial photographs were interpreted for the creation of a
bathymetric grid file to be used for hydrodynamic modelling of the estuary.

The 3DD numerical model was used to determine tidal flows and current velocities. From this initial hydrodynamic model a particle-tracking model was created to determine sediment transport pathways within the estuary. From the initial 20 m model it was then possible to create a number of nested model grids for the purpose of determining the best practice scenario for the
creation of a proposed boat ramp and associated approach channel near the harbour entrance. Hydrodynamic results suggest that residual circulation in Whitianga Estuary is nearly in balance, with a low ebb tidal domination present. Particle tracking results suggest that sediment entrained and carried into and within the estuary will accumulate on the intertidal flats. Sediment
transport modelling indicates that the impact of a proposed boat-ramp will result in sedimentation of the dredged approach channel due to reductions in residual and tidal velocities.

text: Sedimentation And Hydrodynamics of Whitianga Estuary Whitianga Estuary is a bayhead barrier type estuary located on the east of the Coromandel Peninsula, North Island, New Zealand. The catchment has undergone many land-use changes since pre-European settlement. In some areas of the catchment land-use has changed from native forest to grasslands to forestry and back to pasture. These changes in catchment land-use all contribute to increased sedimentation into the estuary. Development of the estuary itself has also occurred in recent times. Much growth has been focussed around the estuary due to Whitianga town-ship having a large boating community, and includes a 170 berth marina and wharf situated at
the tidal inlet entrance to the estuary. These, and the extensive canal development engineering works can have substantial impacts on the
sedimentation regime, and may modify tidal circulation, flushing, and sediment deposition within the estuary.

The principle aim of this research is to assess hydrodynamics and sedimentation of the estuary for future management and development purposes, and also to model different scenarios in order to determine the most cost effective, and least obtrusive design for a proposed boat-ramp and
approach channel near the marina.

To determine sedimentation rates, sediment cores from four locations were collected to depths of 1 m. Coring locations were chosen based on
preliminary model run results, selecting areas that appeared to be long-term sediment sinks of a stable nature. Cores were divided into 10 mm sections and prepared for 210Pb dating and heavy metal analysis, to make an assessment of the vertical sedimentation rates. Recent sedimentation rates were found to be as high as 9 mm/yr post-1950s and past sedimentation rates
as high as 30 mm/yr pre-1950s. The use of heavy metal analysis for dating proved difficult as the background levels of the conservative elements used to normalise results varied, making the geochemical analysis approach inappropriate.

As bathymetry is one of the most important aspects of modelling, a large amount of surveying was undertaken for this study. LiDAR, singlebeam data, and recent rectified aerial photographs were interpreted for the creation of a
bathymetric grid file to be used for hydrodynamic modelling of the estuary.

The 3DD numerical model was used to determine tidal flows and current velocities. From this initial hydrodynamic model a particle-tracking model was created to determine sediment transport pathways within the estuary. From the initial 20 m model it was then possible to create a number of nested model grids for the purpose of determining the best practice scenario for the
creation of a proposed boat ramp and associated approach channel near the harbour entrance. Hydrodynamic results suggest that residual circulation in Whitianga Estuary is nearly in balance, with a low ebb tidal domination present. Particle tracking results suggest that sediment entrained and carried into and within the estuary will accumulate on the intertidal flats. Sediment
transport modelling indicates that the impact of a proposed boat-ramp will result in sedimentation of the dredged approach channel due to reductions in residual and tidal velocities.

year: 2008

title: Epidemiological evidence that can help to improve timely diagnosis of colorectal cancer in New Zealand.

authors: Hirsz, Malgorzata

subjects: Colorectal cancer

abstract: Incidence rates of colorectal cancer (CRC) in New Zealand (NZ) are among the highest in the world. The long-term survival rates in NZ are poor, which has partially been attributed to late diagnosis. Considering that CRC is a curable disease if diagnosed early, conducting research targeted at the improvement of early diagnosis is therefore important. This thesis provides statistical models for the calculation of CRC incidence rates in the entire NZ population and population strata defined by age, gender, ethnicity and diabetes status, and a model for CRC risk in individual patients referred to the secondary care. The models presented here could assist health professionals in the selection of patients for further investigation to facilitate earlier diagnosis. The empirical part consists of three independent observational studies, briefly described below.

Sub-study 1. The objectives were, first, to describe trends in CRC incidence in the NZ population and, second, to investigate whether there are any strata defined by gender and ethnicity with especially increased incidence rates of CRC. To address these objectives, I analysed data from the New Zealand Cancer Registry (years 1994–2018) using an age- period-cohort (APC) model. The overall CRC incidence rates in NZ decreased between 1994 and 2018 by an average of 1.31% per year. However, the decrease was observed only in patients 50 years and older. In those 30-<50 years old, the incidence rates increased between 1994 and 2018 regardless of gender and ethnicity. The increase was similar for proximal, distal and rectal cancers. The APC analyses revealed very strong cohort effects that could explain nearly the entire trends in CRC incidence, pointing out generations born in the 1970s and 80s being affected by the increased incidence rates, rather than individuals 30-<50 years old. The cohort effects were different in Ma ̄ori and non-Ma ̄ori populations. In non-Ma ̄ori born between approximately 1939 and 1955, incidence rates decreased sharply. By contrast, those Ma ̄ori generations have not benefitted from the sharp decrease in rates. However, CRC incidence increased substantially in both M ̄aori and non-M ̄aori groups born in the 1970s and 80s.

Sub-study 2. The objective was to estimate the IRR for CRC in patients with diabetes compared to those without diabetes, with relation to diabetes duration and use of insulin for diabetes control. Registration in the Virtual Diabetes Register (VDR) in the years 2014–2018 was used as a marker of a diabetes diagnosis. Tables with counts of the entire NZ population stratified by age, gender, and ethnicity were obtained from Statistics NZ. In total, data from 310,710 patients with diabetes, corresponding to 1,277,284 person- years and 2512 incident CRC cases were analysed using a Poisson regression model. Diabetes was associated with an overall increased CRC incidence of 13% compared to non-diabetes [IRR=1.13 (95% CI: 1.08, 1.18)]. The IRR was especially high in the first three months after diabetes diagnosis [IRR=2.55 (95% CI 2.02, 3.21)], likely due to detection bias. The association was equally strong in males and females. However, in the analysis by ethnicity, the incidence of CRC was increased only in non-Ma ̄ori patients and restricted only to those younger than 75 years.

Sub-study 3. The objective was to develop a predictive model for CRC risk in individual patients referred to secondary care. To develop such a model, I extracted information from free text included in e-referrals from GPs’ to the Gastroenterology and General Surgery departments in the Waikato Hospital from 2015-2018, including: symptoms; test results; and family history of CRC. The reference test was a full colonoscopy with visualisation of the cecum. Data from 3015 patients, 20-<90 years old were analysed using a logistic regression model. The final model included the following predictors associated with increased CRC risk: anaemia, rectal bleeding, palpable mass in abdomen or rectum, weight loss, age and gender, and a decreased CRC risk: family history of CRC, abdominal pain, and inflammatory bowel disease. The model discriminates patients with low CRC risk well. According to the final cross-validated model, around 20% of patients from our cohort had performed colonoscopy despite a very low CRC risk (less than 1.5%).

In conclusion, the APC analysis revealed an alarming pattern. According to the fitted APC model, the combination of increasing age and cohort effect in generations born in the 1970s and 80s will bring a wave of CRC diagnoses in the near future when the young generations with high CRC incidence rates will replace the old generations with low CRC incidence. The results from this study could therefore help policy-makers to plan the needs for gastroenterology services.
Secondly, CRC incidence rates in diabetes have been found to be slightly increased com- pared to non-diabetes but only in non-Ma ̄ori individuals younger than 75 years.
Third, the results suggest that males underutilise health services. As shown in sub- study 3, males underwent fewer colonoscopies than females, despite having a higher risk of CRC. The higher detection bias in males than in females (sub-study 2) could also suggest underuse of health services by males, but the difference was not statistically significant.
Finally, based on the fitted models for CRC incidence in sub-studies 1 and 2, population- wide CRC screening for Ma ̄ori and patients with diabetes, based on the incidence, instead of age alone, would be proposed to start at age 57.5 years if the screening in the general population starts at age 60 years.

text: Epidemiological evidence that can help to improve timely diagnosis of colorectal cancer in New Zealand. Incidence rates of colorectal cancer (CRC) in New Zealand (NZ) are among the highest in the world. The long-term survival rates in NZ are poor, which has partially been attributed to late diagnosis. Considering that CRC is a curable disease if diagnosed early, conducting research targeted at the improvement of early diagnosis is therefore important. This thesis provides statistical models for the calculation of CRC incidence rates in the entire NZ population and population strata defined by age, gender, ethnicity and diabetes status, and a model for CRC risk in individual patients referred to the secondary care. The models presented here could assist health professionals in the selection of patients for further investigation to facilitate earlier diagnosis. The empirical part consists of three independent observational studies, briefly described below.

Sub-study 1. The objectives were, first, to describe trends in CRC incidence in the NZ population and, second, to investigate whether there are any strata defined by gender and ethnicity with especially increased incidence rates of CRC. To address these objectives, I analysed data from the New Zealand Cancer Registry (years 1994–2018) using an age- period-cohort (APC) model. The overall CRC incidence rates in NZ decreased between 1994 and 2018 by an average of 1.31% per year. However, the decrease was observed only in patients 50 years and older. In those 30-<50 years old, the incidence rates increased between 1994 and 2018 regardless of gender and ethnicity. The increase was similar for proximal, distal and rectal cancers. The APC analyses revealed very strong cohort effects that could explain nearly the entire trends in CRC incidence, pointing out generations born in the 1970s and 80s being affected by the increased incidence rates, rather than individuals 30-<50 years old. The cohort effects were different in Ma ̄ori and non-Ma ̄ori populations. In non-Ma ̄ori born between approximately 1939 and 1955, incidence rates decreased sharply. By contrast, those Ma ̄ori generations have not benefitted from the sharp decrease in rates. However, CRC incidence increased substantially in both M ̄aori and non-M ̄aori groups born in the 1970s and 80s.

Sub-study 2. The objective was to estimate the IRR for CRC in patients with diabetes compared to those without diabetes, with relation to diabetes duration and use of insulin for diabetes control. Registration in the Virtual Diabetes Register (VDR) in the years 2014–2018 was used as a marker of a diabetes diagnosis. Tables with counts of the entire NZ population stratified by age, gender, and ethnicity were obtained from Statistics NZ. In total, data from 310,710 patients with diabetes, corresponding to 1,277,284 person- years and 2512 incident CRC cases were analysed using a Poisson regression model. Diabetes was associated with an overall increased CRC incidence of 13% compared to non-diabetes [IRR=1.13 (95% CI: 1.08, 1.18)]. The IRR was especially high in the first three months after diabetes diagnosis [IRR=2.55 (95% CI 2.02, 3.21)], likely due to detection bias. The association was equally strong in males and females. However, in the analysis by ethnicity, the incidence of CRC was increased only in non-Ma ̄ori patients and restricted only to those younger than 75 years.

Sub-study 3. The objective was to develop a predictive model for CRC risk in individual patients referred to secondary care. To develop such a model, I extracted information from free text included in e-referrals from GPs’ to the Gastroenterology and General Surgery departments in the Waikato Hospital from 2015-2018, including: symptoms; test results; and family history of CRC. The reference test was a full colonoscopy with visualisation of the cecum. Data from 3015 patients, 20-<90 years old were analysed using a logistic regression model. The final model included the following predictors associated with increased CRC risk: anaemia, rectal bleeding, palpable mass in abdomen or rectum, weight loss, age and gender, and a decreased CRC risk: family history of CRC, abdominal pain, and inflammatory bowel disease. The model discriminates patients with low CRC risk well. According to the final cross-validated model, around 20% of patients from our cohort had performed colonoscopy despite a very low CRC risk (less than 1.5%).

In conclusion, the APC analysis revealed an alarming pattern. According to the fitted APC model, the combination of increasing age and cohort effect in generations born in the 1970s and 80s will bring a wave of CRC diagnoses in the near future when the young generations with high CRC incidence rates will replace the old generations with low CRC incidence. The results from this study could therefore help policy-makers to plan the needs for gastroenterology services.
Secondly, CRC incidence rates in diabetes have been found to be slightly increased com- pared to non-diabetes but only in non-Ma ̄ori individuals younger than 75 years.
Third, the results suggest that males underutilise health services. As shown in sub- study 3, males underwent fewer colonoscopies than females, despite having a higher risk of CRC. The higher detection bias in males than in females (sub-study 2) could also suggest underuse of health services by males, but the difference was not statistically significant.
Finally, based on the fitted models for CRC incidence in sub-studies 1 and 2, population- wide CRC screening for Ma ̄ori and patients with diabetes, based on the incidence, instead of age alone, would be proposed to start at age 57.5 years if the screening in the general population starts at age 60 years.

year: 2021