Microbial life and deposits in paper machine circuits

Väitöskirjani käsittele mikrobien ja erilaisten kemikaalien rooleja saostumien ja biofilmien muodostumisessa paperi- ja kartonkikoneilla. "Saostuma" tässä työssä tarkoittaa kiinteän aineen kertymää konepinnoille tai rajapinnoille konekierroissa, jotka on tarkoitettu massasulppujen, lietteiden, vesien tai ilman kuljetukseen. Saostumasta tulee "biofilmi" silloin kun sen oleellinen rakennekomponentti on mikrobisolut tai niiden tuotteet. Väitöstyöni työhypoteesina oli, että i. tietämys saostumien koostumuksesta, sekä ii. niiden rakenteesta, biologisista, fysikaalis-kemiallisista ja teknisistä ominaisuuksista ohjaavat tutkijaa löytämään ympäristöä säästäviä keinoja estää epätoivottujen saostumien muodostus tai purkaa jo muodostuneita saostumia. Selvittääkseni saostumien koostumista ja rakennetta käytin monia erilaisia analytiikan työkaluja, kuten elektronimikroskopiaa, konfokaali-laser mikroskopiaa (CLSM), energiadispersiivistä röntgenanalyysiä (EDX), pyrolyysi kaasukromatografiaa yhdistettynä massaspektrometriaan (Py-GCMS), joninvaihtokromatografiaa, kaasukromatografiaa ja mikrobiologisia analyysejä. Osallistuin aktiivisesti innovatiivisen, valon takaisinsirontaan perustuvan sensorin kehittämistyöhön, käytettäväksi biofilmin kasvun mittaukseen suoraan koneen vesikierroista ja säiliöistä. Työni osoitti, että monet paperinvalmistuksessa käytetyistä kemikaaleista reagoivat keskenään tuottaen orgaanisia tahmakerroksia konekiertojen teräspinnoille. Löysin myös kerrostumia, jotka valomikroskooppisessa tarkastelussa oli tulkittu mikrobeiksi, mutta jotka elektronimikroskopia paljasti alunasta syntyneiksi, alumiinihydroksidiksi joka saostui pH:ssa 6,8 kiertokuitua käyttävän koneen viiravesistä. Monet paperintekijät käyttävät vieläkin alunaa kiinnitysaineena vaikka prosessiolot ovat muuttuneet happamista neutraaleiksi. Sitä pidetään paperitekijän "aspiriinina", mutta väitöstutkimukseni osoitti sen riskit. Löysin myös orgaanisia saostumia, joiden alkuperä oli aineiden, kuten pihkan, saippuoituminen (kalsium saippuat) niin että muodostui tahmankasvua ylläpitävä alusta monilla paperi- ja kartonkikoneilla. Näin solumuodoiltaan Deinococcus geothermalista muistuttavia bakteereita kasvamassa lujasti teräskoepalojen pintaan kiinnittyneinä pesäkkeinä, kun koepaloja upotettiin paperikoneiden vesikiertoihin. Nämä deinokokkimaiset pesäkkeet voivat toimia jalustana, tarttumisalustana muiden mikrobien massoille, joka selittäisi miksi saostumat yleisesti sisältävät deinokokkeja pienenä, muttei koskaan pääasiallisena rakenneosana. Kun paperikoneiden käyttämien vesien (raakavedet, lämminvesi, biologisesti puhdistettu jätevesi) laatua tutkitaan, mittausmenetelmällä on suuri merkitys. Koepalan upotusmenetelmällä todettu biofilmikasvu ja viljelmenetelmällä mitattu bakteerisaastuneisuus korreloivat toisiinsa huonosti etenkin silloin kun likaantumisessa oli mukana rihmamaiseti kasvavia bakteereja. Huoli ympäristöstä on pakottanut paperi- ja kartonkikoneiden vesikiertojen sulkemiseen. Vesien kierrätys ja prosessivesien uudelleenkäyttö nostavat prosessilämpötilaa ja lisäävät koneella kiertävien kolloidisten ja liuenneiden aineiden määriä. Tutkin kiertovesien pitoisuuksia kolmessa eriasteisesti suljetussa tehtaassa, joiden päästöt olivat 0 m3, 0,5 m3 ja 4 m3 jätevettä tuotetonnia kohden, perustuen puhdistetun jäteveden uudelleen käyttöön. Nollapäästöisellä tehtaalla kiertovesiin kertyi paljon orgaanisesti sidottua hiiltä (> 10 g L-1), etenkin haihtuvina happoina (maito-, etikka-, propioni- ja voi-). Myös sulfaatteja, klorideja, natriumia ja kalsiumia kertyi paljon, > 1 g L-1 kutakin. Pääosa (>40%) kaikista bakteereista oli 16S rRNA geenisekvenssianalyysien tulosten perusteella sukua, joskin etäistä (< 96%) ainoastaan Enterococcus cecorum bakteerille. 4 m3 päästävältä tehtaalta löytyi lisäksi Bacillus thermoamylovorans ja Bacillus coagulans. Tehtaiden saostumat sisälsivät arkkeja suurina pitoisuuksina, ≥ 108 g-1, mutta tunnistukseen riittävää sekvenssisamanlaisuutta löytyi vain yhteen arkkisukuun, Methanothrix. Tutkimustulokset osoittivat että tehtaan vesikiertojen sulkeminen vähensi rajusti mikrobiston monimuotoisuutta, muttei estänyt liuenneen aineen ja kiintoaineen mineralisoitumista.

Environmental and fishing effects on the dynamics of brown tiger prawn (Penaeus esculentus) in Moreton Bay (Australia)

This analysis of the variations of brown tiger prawn (Penaeus esculentus) catch in Moreton Bay multispecies trawl fishery estimated catchability using a delay difference model. It integrated several factors responsible for variations in catchability: targeting of fishing effort, increasing fishing power and changing availability. An analysis of covariance was used to define fishing events targeted at brown tiger prawns. A general linear model estimated inter-annual variations of fishing power. Temperature-induced changes in prawn behaviour played an important role on the dynamics of this fishery. Maximum likelihood estimates of targeted catchability (4.09 ± 0.42 × 10−4 boat-day−1) were twice as large as non-targeted catchability (1.86 ± 0.25 × 10−4 boat-day−1). The causes of recent declines in fishing effort in this fishery were discussed.

Modulation of succinate dehydrogenase in response to environmental stress conditions of hypobaria and hypoxia

1. 1. An increase in the oxidation of succinate by hepatic mitochondria in rats exposed to hypoxia (O2-N2; 1:9, v/v) or hypobaria (0.5 atm) was observed which appears to be due to modification of the activity of the rate-limiting succinate dehydrogenase [succinate: (acceptor) oxidoreductase, EC 1.3.99.1].

Concentrations of phthalates and DINCH metabolites in pooled urine from Queensland, Australia

Dialkyl phthalate esters (phthalates) are ubiquitous chemicals used extensively as plasticizers, solvents and adhesives in a range of industrial and consumer products. 1,2-Cyclohexane dicarboxylic acid, diisononyl ester (DINCH) is a phthalate alternative introduced due to a more favourable toxicological profile, but exposure is largely uncharacterised. The aim of this study was to provide the first assessment of exposure to phthalates and DINCH in the general Australian population. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100). Concentrations of free and total species were measured using online solid phase extraction isotope dilution high performance liquid chromatography tandem mass spectrometry. Concentrations ranged from 2.4 to 71.9 ng/mL for metabolites of di(2-ethylhexyl)phthalate, and from < 0.5 to 775 ng/mL for all other metabolites. Our data suggest that phthalate metabolites concentrations in Australia were at least two times higher than in the United States and Germany; and may be related to legislative differences among countries. DINCH metabolite concentrations were comparatively low and consistent with the limited data available. Ongoing biomonitoring among the general Australian population may help assess temporal trends in exposure and assess the effectiveness of actions aimed at reducing exposures.

Assessing infant exposure to persistent organic pollutants via dietary intake in Australia

Persistent organic pollutants (POPs) including polybrominated diphenyl ethers (PBDEs); organochlorine pesticides (OCPs); and polychlorinated biphenyls (PCBs) persist in the environment, bioaccumulate, and pose a risk of causing adverse human health effects. Typically, exposure assessments undertaken by modeling existing intake data underestimate the concentrations of these chemicals in infants. This study aimed to determine concentrations of POPs in infant foods, assess exposure via dietary intake and compare this to historical exposure. Fruit purees, meat and vegetables, dairy desserts, cereals and jelly foods (n = 33) purchased in 2013 in Brisbane, Australia were analyzed. For OCPs and PCBs, concentrations ranged up to 95 pg/g fw and for PBDEs up to 32 pg/g fw with most analytes below the limit of detection. Daily intake is dependent on type and quantity of foods consumed. Consumption of a 140 g meal would result in intake ranging from 0 to 4.2 ng/day, 4.4 ng/day and 13.3 ng/day, for OCPs, PBDEs and PCBs, respectively. PBDEs were detected in 3/33 samples, OCPs in 9/33 samples and PCBs in 13/33 samples. Results from this study indicate exposure for infants via dietary (in contrast to dust and breast milk) intake in Australia contribute only a minor component to total exposure.

Pro-Environmental Organizational Culture and Climate

This chapter reviews the concepts of organizational culture and climate and applies them to environmental sustainability. Though culture and climate are often used interchangeably, the chapter identifies key distinctions between them and highlights how they can complement one another. The two concepts are used to discuss how the organizational context for environmental sustainability, and employee perceptions thereof, influence individual pro-environmental behavior. Organizational climate is integrated with a dynamic model of organizational culture to describe how pro-environmental cultures and climates emerge. The chapter also highlights how organizations with different motivations can create pro-environmental cultures and climates. The chapter uses the Sierra Nevada Brewing Company as an archetype of an organization with a pro-environmental culture and climate. In the course of the discussion, the chapter nominates several imperatives for research and recommendations for practice.

Development and testing of allometric equations for estimating above-ground biomass of mixed-species environmental plantings

To quantify the impact that planting indigenous trees and shrubs in mixed communities (environmental plantings) have on net sequestration of carbon and other environmental or commercial benefits, precise and non-biased estimates of biomass are required. Because these plantings consist of several species, estimation of their biomass through allometric relationships is a challenging task. We explored methods to accurately estimate biomass through harvesting 3139 trees and shrubs from 22 plantings, and collating similar datasets from earlier studies, in non-arid (>300mm rainfallyear-1) regions of southern and eastern Australia. Site-and-species specific allometric equations were developed, as were three types of generalised, multi-site, allometric equations based on categories of species and growth-habits: (i) species-specific, (ii) genus and growth-habit, and (iii) universal growth-habit irrespective of genus. Biomass was measured at plot level at eight contrasting sites to test the accuracy of prediction of tonnes dry matter of above-ground biomass per hectare using different classes of allometric equations. A finer-scale analysis tested performance of these at an individual-tree level across a wider range of sites. Although the percentage error in prediction could be high at a given site (up to 45%), it was relatively low (<11%) when generalised allometry-predictions of biomass was used to make regional- or estate-level estimates across a range of sites. Precision, and thus accuracy, increased slightly with the level of specificity of allometry. Inclusion of site-specific factors in generic equations increased efficiency of prediction of above-ground biomass by as much as 8%. Site-and-species-specific equations are the most accurate for site-based predictions. Generic allometric equations developed here, particularly the generic species-specific equations, can be confidently applied to provide regional- or estate-level estimates of above-ground biomass and carbon. © 2013 Elsevier B.V.

Bentonite can decrease ammonia volatilisation losses from poultry litter: laboratory studies

Ammonia volatilisation from manure materials within poultry sheds can adversely affect production, and also represents a loss of fertiliser value from the spent litter. This study sought to compare the ability of alum and bentonite to decrease volatilisation losses of ammonia from spent poultry litter. An in-vessel volatilisation trial with air flushing, ammonia collection, and ammonia analysis was conducted over 64 days to evaluate the mitigation potential of these two materials. Water-saturated spent litter was incubated at 25°C in untreated condition (control) or with three treatments: an industry-accepted rate of alum [4% Al2(SO4)3·18H2O by dry mass of litter dry mass; ALUM], air-dry bentonite (127% by dry mass; BENT), or water-saturated bentonite (once again at 127% by dry mass; SATBENT). A high proportion of the nitrogen contained in the untreated spent litter was volatilised (62%). Bentonite additions were superior to alum additions at retaining spent litter ammonia (nitrogen losses: 15%, SATBENT; 34%, BENT; 54%, ALUM). Where production considerations favour comparable high rates of bentonite addition (e.g. where the litter is to be re-formulated as a fertiliser), this clay has potential to decrease ammonia volatilisation either in-shed or in spent litter stockpiles or formulated products, without the associated detrimental effect of alum on phosphorus availability.

A physiological framework to explain genetic and environmental regulation of tillering in sorghum

Tillering determines the plant size of sorghum (Sorghum bicolor) and an understanding of its regulation is important to match genotypes to prevalent growing conditions in target production environments. The aim of this study was to determine the physiological and environmental regulation of variability in tillering among sorghum genotypes, and to develop a framework for this regulation. * Diverse sorghum genotypes were grown in three experiments with contrasting temperature, radiation and plant density to create variation in tillering. Data on phenology, tillering, and leaf and plant size were collected. A carbohydrate supply/demand (S/D) index that incorporated environmental and genotypic parameters was developed to represent the effects of assimilate availability on tillering. Genotypic differences in tillering not explained by this index were defined as propensity to tiller (PTT) and probably represented hormonal effects. * Genotypic variation in tillering was associated with differences in leaf width, stem diameter and PTT. The S/D index captured most of the environmental effects on tillering and PTT most of the genotypic effects. * A framework that captures genetic and environmental regulation of tillering through assimilate availability and PTT was developed, and provides a basis for the development of a model that connects genetic control of tillering to its phenotypic consequences.

Potential Animal and Environmental Sources of Q Fever Infection for Humans in Queensland

Q fever is a vaccine-preventable disease; despite this, high annual notification numbers are still recorded in Australia. We have previously shown seroprevalence in Queensland metropolitan regions is approaching that of rural areas. This study investigated the presence of nucleic acid from Coxiella burnetii, the agent responsible for Q fever, in a number of animal and environmental samples collected throughout Queensland, to identify potential sources of human infection. Samples were collected from 129 geographical locations and included urine, faeces and whole blood from 22 different animal species; 45 ticks were removed from two species, canines and possums; 151 soil samples; 72 atmospheric dust samples collected from two locations and 50 dust swabs collected from domestic vacuum cleaners. PCR testing was performed targeting the IS1111 and COM1 genes for the specific detection of C.burnetii DNA. There were 85 detections from 1318 animal samples, giving a detection rate for each sample type ranging from 2.1 to 6.8%. Equine samples produced a detection rate of 11.9%, whilst feline and canine samples showed detection rates of 7.8% and 5.2%, respectively. Native animals had varying detection rates: pooled urines from flying foxes had 7.8%, whilst koalas had 5.1%, and 6.7% of ticks screened were positive. The soil and dust samples showed the presence of C.burnetii DNA ranging from 2.0 to 6.9%, respectively. These data show that specimens from a variety of animal species and the general environment provide a number of potential sources for C.burnetii infections of humans living in Queensland. These previously unrecognized sources may account for the high seroprevalence rates seen in putative low-risk communities, including Q fever patients with no direct animal contact and those subjects living in a low-risk urban environment.

Use of pooled samples to assess human exposure to parabens, benzophenone-3 and triclosan in Queensland, Australia

Parabens, benzophenone-3 and triclosan are common ingredients used as preservatives, ultraviolet radiation filters and antimicrobial agents, respectively. Human exposure occurs through consumption of processed food and use of cosmetics and consumer products. The aim of this study was to provide a preliminary characterisation of exposure to selected personal care product chemicals in the general Australian population. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n= 24 pools of 100). Concentrations of free and total (sum of free plus conjugated) species of methyl, ethyl, propyl and butyl paraben, benzophenone-3 and triclosan were quantified using isotope dilution tandem mass spectrometry; with geometric means 232, 33.5, 60.6, 4.32, 61.5 and 87.7. ng/mL, respectively. Age was inversely associated with paraben concentration, and females had concentrations approximately two times higher than males. Total paraben and benzophenone-3 concentrations are significantly higher than reported worldwide, and the average triclosan concentration was more than one order of magnitude higher than in many other populations. This study provides the first data on exposure of the general Australian population to a range of common personal care product chemical ingredients, which appears to be prevalent and warrants further investigation.

Persistent organic pollutants in matched breast milk and infant faeces samples

Assessing blood concentration of persistent organic pollutants (POPs) in infants is difficult due to the ethical and practical difficulties in obtaining sufficient quantities of blood. To determine whether measuring POPs in faeces might reflect blood concentration during infancy, we measured the concentrations of a range of POPs (i.e. polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs)) in a pilot study using matched breast milk and infant faecal samples obtained from ten mother-child pairs. All infants were breast fed, with 8 of them also receiving solid food at the time of faecal sampling. In this small dataset faecal concentrations (range 0.01-41ngg-1 lipid) are strongly associated with milk concentrations (range 0.02-230ngg-1 lipid). Associations with other factors generally could not be detected in this dataset, with the exception of a small effect of age or growth. Different sources (external or internal) of exposure appeared to directly influence faecal concentrations of different chemicals based on different inter-individual variability in the faeces-to-milk concentration ratio Rfm. Overall, the matrix of faeces as an external measure of internal exposure in infants looks promising for some chemicals and is worth assessing further in larger datasets.

Novel fluorinated surfactants tentatively identified in firefighters using liquid chromatography quadrupole time-of flight tandem mass spectrometry and a case-control approach

Fluorinated surfactant-based aqueous film-forming foams (AFFFs) are made up of per- and polyfluorinated alkyl substances (PFAS) and are used to extinguish fires involving highly flammable liquids. The use of perfluorooctanesulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in some AFFF formulations has been linked to substantial environmental contamination. Recent studies have identified a large number of novel and infrequently reported fluorinated surfactants in different AFFF formulations. In this study, a strategy based on a case-control approach using quadrupole time-of-flight tandem mass spectrometry (QTOF-MS/MS) and advanced statistical methods has been used to extract and identify known and unknown PFAS in human serum associated with AFFF-exposed firefighters. Two target sulfonic acids [PFOS and perfluorohexanesulfonic acid (PFHxS)], three non-target acids [perfluoropentanesulfonic acid (PFPeS), perfluoroheptanesulfonic acid (PFHpS), and perfluorononanesulfonic acid (PFNS)], and four unknown sulfonic acids (Cl-PFOS, ketone-PFOS, ether-PFHxS, and Cl-PFHxS) were exclusively or significantly more frequently detected at higher levels in firefighters compared to controls. The application of this strategy has allowed for identification of previously unreported fluorinated chemicals in a timely and cost-efficient way.

Miniaturized mass spectrometric ionization techniques for environmental analysis and bioanalysis

Miniaturized mass spectrometric ionization techniques for environmental analysis and bioanalysis Novel miniaturized mass spectrometric ionization techniques based on atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) were studied and evaluated in the analysis of environmental samples and biosamples. The three analytical systems investigated here were gas chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry (GC-µAPCI-MS) and gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry (GC-µAPPI-MS), where sample pretreatment and chromatographic separation precede ionization, and desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS), where the samples are analyzed either as such or after minimal pretreatment. The gas chromatography-microchip atmospheric pressure ionization-mass spectrometry (GC-µAPI-MS) instrumentations were used in the analysis of polychlorinated biphenyls (PCBs) in negative ion mode and 2-quinolinone-derived selective androgen receptor modulators (SARMs) in positive ion mode. The analytical characteristics (i.e., limits of detection, linear ranges, and repeatabilities) of the methods were evaluated with PCB standards and SARMs in urine. All methods showed good analytical characteristics and potential for quantitative environmental analysis or bioanalysis. Desorption and ionization mechanisms in DAPPI were studied. Desorption was found to be a thermal process, with the efficiency strongly depending on thermal conductivity of the sampling surface. Probably the size and polarity of the analyte also play a role. In positive ion mode, the ionization is dependent on the ionization energy and proton affinity of the analyte and the spray solvent, while in negative ion mode the ionization mechanism is determined by the electron affinity and gas-phase acidity of the analyte and the spray solvent. DAPPI-MS was tested in the fast screening analysis of environmental, food, and forensic samples, and the results demonstrated the feasibility of DAPPI-MS for rapid screening analysis of authentic samples.