title: Fate and effects of pulp mill effluent solids in the soil environment

authors: Fraser, Donald Scott

subjects: pulp mill effluent

abstract: The pulp and paper industry in New Zealand annually produces over one hundred thousand dry tonnes of solid waste due to the treatment of pulp and paper mill effluents, the majority of which is currently landfilled. The New Zealand Waste Management Strategy (2002) has set a target for  the diversion of commercial organic wastes from landfill to beneficial use to exceed 95% by 2010 . 

Effluents produced by softwood pulp mills, such as in New Zealand, contain high concentrations of naturally derived resin extractive compounds that are toxic to fish and other aquatic organisms. Improvements in waste water treatment technology has enabled the industry to meet rigorous discharge standards, however, this has resulted in an increase in the production of pulp mill effluent solids which require disposal. This has become an issue for the pulp and paper industry, especially as current landfill space is limited. Land application has been used for many years as a means of disposal of pulp mill wastes. While most studies investigating land application of pulp mill effluent solids have concluded that the risk posed to the environment is low, few have investigated the potential toxicity of these wastes to soil organisms, and these studies did not directly address the effects of resin extractive compounds. 

Resin extractives have been shown to be recalcitrant and to accumulate in anaerobic sediments. It is not known to what extent resin extractives are bioavailable or degradable in land applied Pulp mill effluent solids (PMES), or their potential to bioaccumulate in soil organisms.

This PhD thesis research sought to extend the knowledge on the environmental fate and effects of pulp mill effluent wastes. It focused on terrestrial systems, which have not been well studied in this respect. Four chemically distinct softwood pulp mill effluent solids, a primary treatment solid and three secondary treatment biosolids, were used to investigate their effects on soil organisms and soil functions. An interdisciplinary approach was adopted, which incorporated three main areas of study, as follows:
1. A comprehensive resin extractives analysis of the pulp mill effluent solids undertaken so that effects on soil organisms and soil functions could be related to the resin extractives chemistry of the individual pulp mill effluent solids tested. 
2.  A battery of bioassays used to investigate the toxicity of the selected pulp mill effluent solids. 
3.	A field trial set-up to investigate how pulp mill effluent solids affected soil functions and also to investigate the decomposition of pulp mill effluent solids and of resin extractives in these solids. 

Three hypotheses tested were:
 I. Pulp mill effluent solids are toxic to soil organisms.
II. Resin extractives in pulp mill effluent solids are recalcitrant in the terrestrial environment.
III. Pulp mill effluent solids will cause significant measurable negative impacts on soil functional capacity.

A wide range of resin extractives compounds were identified in pulp mill effluent solids, and concentrations of individual compounds varied widely between the different pulp mill effluent solids tested. During the two years after field application of the pulp mill effluent solids, resin extractives declined, however, decay rates of individual compounds were variable. The decay rate of compounds was influenced by the type of pulp mill effluent solids containing these compounds and not by the initial concentration of compounds. All compounds, including resin acids, degraded rapidly in the applied primary solid and in one of the applied biosolids, with average half-lives calculated ranging from three to twelve months. In the other biosolids, resin acids were recalcitrant with average half-lives calculated to be nearly ten years. 

Laboratory bioassays conducted on oats, earthworms and enchytraeid worms indicated that pulp mill effluent solids had low toxicity to these organisms. An aquatic bioassay organism, however, was acutely affected by aqueous extracts from pulp mill effluent solids. Earthworms were shown to bioaccumulate some resin extractive compounds to a limited extent, indicating that resin extractives were bioavailable in pulp mill effluent solids. Enchytraeid reproduction was reduced by exposure to some pulp mill effluent solids but this was not correlated to resin extractives concentration of the solids tested. 

Field applied pulp mill effluent solids significantly enhanced the fluxes of CO2 from the soil surface. When mass losses of pulp mill effluent solids carbon were taken into account, it was shown that these solids had little effect on soil respiration. Needle litterbags were placed above and below pulp mill effluent solids and in the litter horizon of a control treatment for 12 months. Needle litter decomposition was not significantly different between treatments, however, changes in enzyme activities were detected in litter beneath pulp mill effluent solids compared to control needle litter that had not been exposed to pulp mill effluent solids. The decomposition rate of field applied pulp mill effluent solids was slow, with half-lives extrapolated to be between five and twenty five years. The decomposition rate appeared to be influenced by the pools of carbon available for decomposition, with primary solids decaying significantly faster than biosolids due to a higher cellulose component.

The conclusions of the PhD thesis research are, therefore, that generally, pulp mill effluent solids used in the study were demonstrated to be relatively benign and appear to pose a low risk to the terrestrial ecosystem when applied to soil. However, a cautious approach is still recommended to land application, based on the extensive evidence of disruption to aquatic ecosystems, and because pulp mill effluent solids will take many years to decompose and resin acids are recalcitrant in some pulp mill effluent solids. Further research is recommended to elucidate mechanisms of action by resin extractives in soil organisms and the ultimate fate of these compounds in the soil compartment.

text: Fate and effects of pulp mill effluent solids in the soil environment The pulp and paper industry in New Zealand annually produces over one hundred thousand dry tonnes of solid waste due to the treatment of pulp and paper mill effluents, the majority of which is currently landfilled. The New Zealand Waste Management Strategy (2002) has set a target for  the diversion of commercial organic wastes from landfill to beneficial use to exceed 95% by 2010 . 

Effluents produced by softwood pulp mills, such as in New Zealand, contain high concentrations of naturally derived resin extractive compounds that are toxic to fish and other aquatic organisms. Improvements in waste water treatment technology has enabled the industry to meet rigorous discharge standards, however, this has resulted in an increase in the production of pulp mill effluent solids which require disposal. This has become an issue for the pulp and paper industry, especially as current landfill space is limited. Land application has been used for many years as a means of disposal of pulp mill wastes. While most studies investigating land application of pulp mill effluent solids have concluded that the risk posed to the environment is low, few have investigated the potential toxicity of these wastes to soil organisms, and these studies did not directly address the effects of resin extractive compounds. 

Resin extractives have been shown to be recalcitrant and to accumulate in anaerobic sediments. It is not known to what extent resin extractives are bioavailable or degradable in land applied Pulp mill effluent solids (PMES), or their potential to bioaccumulate in soil organisms.

This PhD thesis research sought to extend the knowledge on the environmental fate and effects of pulp mill effluent wastes. It focused on terrestrial systems, which have not been well studied in this respect. Four chemically distinct softwood pulp mill effluent solids, a primary treatment solid and three secondary treatment biosolids, were used to investigate their effects on soil organisms and soil functions. An interdisciplinary approach was adopted, which incorporated three main areas of study, as follows:
1. A comprehensive resin extractives analysis of the pulp mill effluent solids undertaken so that effects on soil organisms and soil functions could be related to the resin extractives chemistry of the individual pulp mill effluent solids tested. 
2.  A battery of bioassays used to investigate the toxicity of the selected pulp mill effluent solids. 
3.	A field trial set-up to investigate how pulp mill effluent solids affected soil functions and also to investigate the decomposition of pulp mill effluent solids and of resin extractives in these solids. 

Three hypotheses tested were:
 I. Pulp mill effluent solids are toxic to soil organisms.
II. Resin extractives in pulp mill effluent solids are recalcitrant in the terrestrial environment.
III. Pulp mill effluent solids will cause significant measurable negative impacts on soil functional capacity.

A wide range of resin extractives compounds were identified in pulp mill effluent solids, and concentrations of individual compounds varied widely between the different pulp mill effluent solids tested. During the two years after field application of the pulp mill effluent solids, resin extractives declined, however, decay rates of individual compounds were variable. The decay rate of compounds was influenced by the type of pulp mill effluent solids containing these compounds and not by the initial concentration of compounds. All compounds, including resin acids, degraded rapidly in the applied primary solid and in one of the applied biosolids, with average half-lives calculated ranging from three to twelve months. In the other biosolids, resin acids were recalcitrant with average half-lives calculated to be nearly ten years. 

Laboratory bioassays conducted on oats, earthworms and enchytraeid worms indicated that pulp mill effluent solids had low toxicity to these organisms. An aquatic bioassay organism, however, was acutely affected by aqueous extracts from pulp mill effluent solids. Earthworms were shown to bioaccumulate some resin extractive compounds to a limited extent, indicating that resin extractives were bioavailable in pulp mill effluent solids. Enchytraeid reproduction was reduced by exposure to some pulp mill effluent solids but this was not correlated to resin extractives concentration of the solids tested. 

Field applied pulp mill effluent solids significantly enhanced the fluxes of CO2 from the soil surface. When mass losses of pulp mill effluent solids carbon were taken into account, it was shown that these solids had little effect on soil respiration. Needle litterbags were placed above and below pulp mill effluent solids and in the litter horizon of a control treatment for 12 months. Needle litter decomposition was not significantly different between treatments, however, changes in enzyme activities were detected in litter beneath pulp mill effluent solids compared to control needle litter that had not been exposed to pulp mill effluent solids. The decomposition rate of field applied pulp mill effluent solids was slow, with half-lives extrapolated to be between five and twenty five years. The decomposition rate appeared to be influenced by the pools of carbon available for decomposition, with primary solids decaying significantly faster than biosolids due to a higher cellulose component.

The conclusions of the PhD thesis research are, therefore, that generally, pulp mill effluent solids used in the study were demonstrated to be relatively benign and appear to pose a low risk to the terrestrial ecosystem when applied to soil. However, a cautious approach is still recommended to land application, based on the extensive evidence of disruption to aquatic ecosystems, and because pulp mill effluent solids will take many years to decompose and resin acids are recalcitrant in some pulp mill effluent solids. Further research is recommended to elucidate mechanisms of action by resin extractives in soil organisms and the ultimate fate of these compounds in the soil compartment.

year: 2007

title: Single nucleotide polymorphisms associated with the human electroencephalogram during desflurane anaesthesia

authors: Mulholland, Claire Vignette

subjects: single nucleotide polymorphism

abstract: General anaesthesia is an induced state that enables a person to endure surgical procedures without pain or recollection. There is substantial individual variability in the response to anaesthesia and in order to avoid adverse effects caused by either under- or over-sedation, anaesthetic drug administration must be tailored to suit the individual patient. This requires a means to monitor the depth of general anaesthesia. The electroencephalogram (EEG) records the electrical activity of the brain and enables effects of anaesthetic drugs on brain functioning to be monitored. Quantitative EEG monitors, such as the Bispectral (BIS) index monitor, process the raw EEG and provide a numerical output that is often used to measure the depth of general anaesthesia during surgery. Due to a number of factors including clinical conditions and genetic variability in the EEG, the BIS value can at times be misleading. 

To identify genetic variations associated with EEG phenotypes relevant to anaesthesia monitoring, an association analysis was performed for 34 single nucleotide polymorphisms (SNPs) in a sample of 125 surgical patients undergoing general, gynaecological or orthopaedic surgery. During surgery, patients were anaesthetised with the volatile anaesthetic agent desflurane, the depth of anaesthesia was measured using BIS monitoring and the raw was also EEG recorded. SNP genotyping was performed for 13 SNPs in five candidate genes; SGIP1, GABRA2, CACNA1G, HCN1 and HCN2, using the polymerase chain reaction and restriction fragment length polymorphism analysis. An additional 21 SNPs in 15 genes involved in various inflammatory and other immune-related pathways were genotyped by Sequenom MassARRAY at the Australian Genome Research Facility.
Six SNPs in five different genes were found to be associated with spindle amplitude (SGIP1, GABRA2, HCN1, IL1B and MYD88), and a further five SNPs were associated with either delta frequency (IL10), or end tidal desflurane concentration (ETDC) (CACNA1G, CRP, MYD88 and TGFB1). The strongest associations were identified for a single SNP located in the 3' UTR of MYD88 (rs6853). The rs6853 A/G genotype was associated with higher median spindle amplitude (p = 0.0040) and spindle amplitude relative to ETDC (p = 0.0006), and lower EDTC (p = 0.0095) than the A/A genotype. No rs6853 G/G homozygotes were identified in the study sample.
MYD88 acts as an adaptor protein in the interleukin-1 receptor and toll-like receptor signalling pathways. Within the brain, cytokines are thought to act as neuronal modulators and influence neurotransmitter signalling and ion channel activity. The association of MYD88 with spindle amplitude, in conjunction with IL1B, suggests that cytokines may influence the EEG during general anaesthesia. Thus cytokine mediated regulation of neuronal activity is speculated to underlie the reported associations. All reported effect sizes were small (0.77- to 1.55-fold) and associated genes had four distinct types of function; ion channels, neurotransmitter signalling, endocytosis, and cytokine signalling. This suggests that numerous genes in different pathways, each with a small, possibly additive effect, are involved in regulating the EEG during general anaesthesia.

text: Single nucleotide polymorphisms associated with the human electroencephalogram during desflurane anaesthesia General anaesthesia is an induced state that enables a person to endure surgical procedures without pain or recollection. There is substantial individual variability in the response to anaesthesia and in order to avoid adverse effects caused by either under- or over-sedation, anaesthetic drug administration must be tailored to suit the individual patient. This requires a means to monitor the depth of general anaesthesia. The electroencephalogram (EEG) records the electrical activity of the brain and enables effects of anaesthetic drugs on brain functioning to be monitored. Quantitative EEG monitors, such as the Bispectral (BIS) index monitor, process the raw EEG and provide a numerical output that is often used to measure the depth of general anaesthesia during surgery. Due to a number of factors including clinical conditions and genetic variability in the EEG, the BIS value can at times be misleading. 

To identify genetic variations associated with EEG phenotypes relevant to anaesthesia monitoring, an association analysis was performed for 34 single nucleotide polymorphisms (SNPs) in a sample of 125 surgical patients undergoing general, gynaecological or orthopaedic surgery. During surgery, patients were anaesthetised with the volatile anaesthetic agent desflurane, the depth of anaesthesia was measured using BIS monitoring and the raw was also EEG recorded. SNP genotyping was performed for 13 SNPs in five candidate genes; SGIP1, GABRA2, CACNA1G, HCN1 and HCN2, using the polymerase chain reaction and restriction fragment length polymorphism analysis. An additional 21 SNPs in 15 genes involved in various inflammatory and other immune-related pathways were genotyped by Sequenom MassARRAY at the Australian Genome Research Facility.
Six SNPs in five different genes were found to be associated with spindle amplitude (SGIP1, GABRA2, HCN1, IL1B and MYD88), and a further five SNPs were associated with either delta frequency (IL10), or end tidal desflurane concentration (ETDC) (CACNA1G, CRP, MYD88 and TGFB1). The strongest associations were identified for a single SNP located in the 3' UTR of MYD88 (rs6853). The rs6853 A/G genotype was associated with higher median spindle amplitude (p = 0.0040) and spindle amplitude relative to ETDC (p = 0.0006), and lower EDTC (p = 0.0095) than the A/A genotype. No rs6853 G/G homozygotes were identified in the study sample.
MYD88 acts as an adaptor protein in the interleukin-1 receptor and toll-like receptor signalling pathways. Within the brain, cytokines are thought to act as neuronal modulators and influence neurotransmitter signalling and ion channel activity. The association of MYD88 with spindle amplitude, in conjunction with IL1B, suggests that cytokines may influence the EEG during general anaesthesia. Thus cytokine mediated regulation of neuronal activity is speculated to underlie the reported associations. All reported effect sizes were small (0.77- to 1.55-fold) and associated genes had four distinct types of function; ion channels, neurotransmitter signalling, endocytosis, and cytokine signalling. This suggests that numerous genes in different pathways, each with a small, possibly additive effect, are involved in regulating the EEG during general anaesthesia.

year: 2012

title: Lake Rotokakahi: The kakahi (Hyridella menziesi) in a general framework of lake health

authors: Butterworth, Joseph

subjects: Rotokakahi

abstract: Lake Rotokakahi is a mesotrophic lake located within the Rotorua Lakes District, North Island, New Zealand. Under the legal guardianship of the Tuhourangi and Ngati Tumatawera tribes of Te Arawa it has remained closed to the public since 1948. 

Lake Rotokakahi was last monitored regularly in 1996 under the Environment Bay of Plenty (EBOP) water quality monitoring programme with only the lake outlet (Te Wairoa Stream) being monitored since that time. Water quality data collected up to 1996 suggests that there may be degradation of water quality in the lake, as indicated by declining levels of dissolved oxygen in the bottom waters.

 Lake Rotokakahi steeped in historical significance, as well as having major cultural and recreational values was well known for its abundant resources and as the name suggests, particularly for its massive supply of the freshwater mussel or kakahi (Hyridella menziesi). Freshwater mussel species worldwide are in decline however little is known on factors controlling kakahi abundance and distribution. 

The overarching objective of this thesis is update water quality data last monitored in Lake Rotokakahi in 1996 while also identifying key environmental variables thought to influence kakahi populations.  This objective is underpinned by a number of aims that include:
 	Establishment of a 12-13 month water quality programme within Lake Rotokakahi so that data is obtained for comparisons with previous water quality data (pre-1997) to allow assessment of whether there have been water quality changes in the lake.
 	Conduct a population survey of the resident kakahi population examining possible environmental factors influencing their populations.
 	Present an oral history of Lake Rotokakahi focusing on its historical significance, water quality, and collection of kairoto (food collected form lakes).

from the 18 September 2006 to 14 September 2007 monthly water sampling was carried out at a mid lake station, the lake outflow and inflow for measures of nutrients, phytoplankton, zooplankton and chlorophyll a. Vertical profiles of temperature dissolved oxygen and chlorophyll fluorescence were also taken on various part of Lake Rotokakahi.

A lengthened period of anoxia in the bottom waters during thermal stratification was recorded with increased levels of chlorophyll a in winter and reduced secchi disk depth indicating an increase in phytoplankton biomass. Nutrient concentrations remain moderate relative to historical data. On going water quality monitoring on Lake Rotokakahi is recommended to further evaluate the extent of which water quality change is occurring. This will provide a better understanding of how Lake Rotokakahi can be best managed to further preserve the lake.

On 1 March and 20 April kakahi were sampled at five sites. Large kakahi densities were distributed predominantly in depths above the hypolimnion. Chlorophyll a fluorescence and dissolved oxygen were found to be the best correlates for kakahi density and biomass respectively. Low dissolved oxygen concentrations in the hypolimnion are thought to restrict kakahi distributions to above the thermocline in periods of hypolimnetic anoxia.

text: Lake Rotokakahi: The kakahi (Hyridella menziesi) in a general framework of lake health Lake Rotokakahi is a mesotrophic lake located within the Rotorua Lakes District, North Island, New Zealand. Under the legal guardianship of the Tuhourangi and Ngati Tumatawera tribes of Te Arawa it has remained closed to the public since 1948. 

Lake Rotokakahi was last monitored regularly in 1996 under the Environment Bay of Plenty (EBOP) water quality monitoring programme with only the lake outlet (Te Wairoa Stream) being monitored since that time. Water quality data collected up to 1996 suggests that there may be degradation of water quality in the lake, as indicated by declining levels of dissolved oxygen in the bottom waters.

 Lake Rotokakahi steeped in historical significance, as well as having major cultural and recreational values was well known for its abundant resources and as the name suggests, particularly for its massive supply of the freshwater mussel or kakahi (Hyridella menziesi). Freshwater mussel species worldwide are in decline however little is known on factors controlling kakahi abundance and distribution. 

The overarching objective of this thesis is update water quality data last monitored in Lake Rotokakahi in 1996 while also identifying key environmental variables thought to influence kakahi populations.  This objective is underpinned by a number of aims that include:
 	Establishment of a 12-13 month water quality programme within Lake Rotokakahi so that data is obtained for comparisons with previous water quality data (pre-1997) to allow assessment of whether there have been water quality changes in the lake.
 	Conduct a population survey of the resident kakahi population examining possible environmental factors influencing their populations.
 	Present an oral history of Lake Rotokakahi focusing on its historical significance, water quality, and collection of kairoto (food collected form lakes).

from the 18 September 2006 to 14 September 2007 monthly water sampling was carried out at a mid lake station, the lake outflow and inflow for measures of nutrients, phytoplankton, zooplankton and chlorophyll a. Vertical profiles of temperature dissolved oxygen and chlorophyll fluorescence were also taken on various part of Lake Rotokakahi.

A lengthened period of anoxia in the bottom waters during thermal stratification was recorded with increased levels of chlorophyll a in winter and reduced secchi disk depth indicating an increase in phytoplankton biomass. Nutrient concentrations remain moderate relative to historical data. On going water quality monitoring on Lake Rotokakahi is recommended to further evaluate the extent of which water quality change is occurring. This will provide a better understanding of how Lake Rotokakahi can be best managed to further preserve the lake.

On 1 March and 20 April kakahi were sampled at five sites. Large kakahi densities were distributed predominantly in depths above the hypolimnion. Chlorophyll a fluorescence and dissolved oxygen were found to be the best correlates for kakahi density and biomass respectively. Low dissolved oxygen concentrations in the hypolimnion are thought to restrict kakahi distributions to above the thermocline in periods of hypolimnetic anoxia.

year: 2008