Bioanalytical and chemical assessment of the disinfection by-product formation potential: Role of organic matter

Disinfection by-products (DBP) formed from natural organic matter and disinfectants like chlorine and chloramine may cause adverse health effects. Here, we evaluate how the quantity and quality of natural organic matter and other precursors influence the formation of DBPs during chlorination and chloramination using a comprehensive approach including chemical analysis of regulated and emerging DBPs, total organic halogen quantification, organic matter characterisation and bioanalytical tools. In vitro bioassays allow us to assess the hazard potential of DBPs early in the chain of cellular events, when the DBPs react with their molecular target(s) and activate stress response and defence mechanisms. Given the reactive properties of known DBPs, a suite of bioassays targeting reactive modes of toxic action including genotoxicity and sensitive early warning endpoints such as protein damage and oxidative stress were evaluated in addition to cytotoxicity. Coagulated surface water was collected from three different drinking water treatment plants, along with reverse osmosis permeate from a desalination plant, and DBP formation potential was assessed after chlorination and chloramination. While effects were low or below the limit of detection before disinfection, the observed effects and DBP levels increased after disinfection and were generally higher after chlorination than after chloramination, indicating that chlorination forms higher concentrations of DBPs or more potent DBPs in the studied waters. Bacterial cytotoxicity, assessed using the bioluminescence inhibition assay, and induction of the oxidative stress response were the most sensitive endpoints, followed by genotoxicity. Source waters with higher dissolved organic carbon levels induced increased DBP formation and caused greater effects in the endpoints related to DNA damage repair, glutathione conjugation/protein damage and the Nrf2 oxidative stress response pathway after disinfection. Fractionation studies indicated that all molecular weight fractions of organic carbon contributed to the DBP formation potential, with the humic rich fractions forming the greatest amount of DBPs, while the low molecular weight fractions formed more brominated DBPs due to the high bromide to organic carbon ratio. The presence of higher bromide concentrations also led to a higher fraction of brominated DBPs as well as proportionally higher effects. This study demonstrates how a suite of analytical and bioanalytical tools can be used to effectively characterise the precursors and formation potential of DBPs.     

A comparison of the quantitative methods for the analysis of the platinum-containing anticancer drug [cis-[amminedichloro(2-methylpyridine)]platinum(II)] (ZD0473) by HPLC coupled to either a triple quadrupole mass spectrometer or an inductively coupled plasma mass spectrometer

The use of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICPMS) as means for the quantitative determination of ZD0473, a platinum anticancer drug, and its related biologically active "aqua" compounds in biofluid samples is described. The performance of the resulting HPLC-ICPMS method was compared with that of a conventional HPLC-triple quadrupole mass spectrometer-based (HPLC-MS/MS) system for properties such as limit of detection, linearity, and reproducibility using spiked samples. The methods were then applied to the determination of plasma ultrafitrate concentrations of ZD0473 in dog plasma samples obtained following intravenous and oral administration at 0.5 and 6 mg/kg, respectively. These experiments showed that both methods were capable of providing accurate and precise results but that the HPLC-ICPMS method had advantages of extended linear range and superior sensitivity, providing a limit of quantification of 0.1 ng/mL for ZD0473, as compared to 5 ng/mL using the current HPLC-MS/MS method. In addition, by using a single combined HPLC-ICPMS/MS/MS system, it was possible to determine the relative MS/MS response of the aqua compounds for the first time.     

A screening level fate model of organic contaminants from advanced water treatment in a potable water supply reservoir

Augmentation of potable water sources by planned indirect potable reuse of wastewater is being widely considered to address growing water shortages. Environmental buffers such as lakes and dams may act as one of a series of barriers to potable water contamination stemming from micropollutants in wastewater. In South-East Queensland, Australia, current government policy is to begin indirect potable reuse of water from reverse osmosis equipped advanced water treatment plants (AWTPs) when the combined capacity of its major storages is at 40% capacity. A total of 15 organic contaminants including NDMA and bisphenol A have been publically reported as detected in recycled water from one of South-East Queensland’s AWTPs, while another 98 chemicals were analysed for, but found to be below their detection limit. To assess the natural attenuation in Lake Wivenhoe, a Level III fugacity based evaluative fate model was constructed using the maximum concentrations of these contaminants detected as input data. A parallel aquivalence based model was constructed for those contaminants, such as dichloroacetic acid, dalapon and triclopyr, which are ionised in the environment of Lake Wivenhoe. A total of 247 organic chemicals of interest, including disinfection by-products, pesticides, pharmaceuticals and personal care products, xenoestrogens and industrial chemicals, were evaluated with the model to assess their potential for natural attenuation. Out of the 15 detected chemicals, trihalomethanes are expected to volatilise with concentrations in the outflow from the dam approximately 400 times lower than influent from the AWTPs. Transformation processes in water are likely to be more significant for NDMA and pharmaceuticals such as salicylic acid and paracetamol as well as for caffeine and the herbicides dalapon and triclopyr. For hydrophobic contaminants such as cholesterol and phenolic xenoestrogens such as 4-nonylphenol, 4-t-octylphenol and bisphenol A, equilibrium between water and sediments will not be attained and hence fate processes such as removal in outflow are predicted to become relatively important.     

Natural versus wastewater derived dissolved organic carbon: implications for the environmental fate of organic micropollutants

The interaction of organic micropollutants with dissolved organic carbon (DOC) can influence their transport, degradation and bioavailability. While this has been well established for natural organic carbon, very little is known regarding the influence of DOC on the fate of micropollutants during wastewater treatment and water recycling. Dissolved organic carbon-water partition coefficients (K_DOC) for wastewater derived and reference DOC were measured for a range of micropollutants using a depletion method with polydimethylsiloxane disks. For micropollutants with an octanol-water partition coefficient (log K_OW) greater than 4 there was a significant difference in K_DOC between reference and wastewater derived DOC, with partitioning to wastewater derived DOC over 1000 times lower for the most hydrophobic micropollutants. The interaction of nonylphenol with wastewater derived DOC from different stages of a wastewater and advanced water treatment train was studied, but little difference in K_DOC was observed. Organic carbon characterisation revealed that reference and wastewater derived DOC had very different properties due to their different origins. Consequently, the reduced sorption capacity of wastewater derived DOC may be related to their microbial origin which led to reduced aromaticity and lower molecular weight. This study suggests that for hydrophobic micropollutants (log K_OW > 4) a higher concentration of freely dissolved and thus bioavailable micropollutants is expected in the presence of wastewater derived DOC than predicted using K_DOC values quantified using reference DOC. The implication is that naturally derived DOC may not be an appropriate surrogate for wastewater derived DOC as a matrix for assessing the fate of micropollutants in engineered systems.     

Antimicrobial and Anticancer Properties of Synthetic Peptides Derived from the Wasp Parachartergus fraternus

Agelaia-MPI and protonectin are antimicrobial peptides isolated from the wasp Parachartergus fraternus that show antimicrobial and neuroactive activities. Previously, two analogues of these peptides, neuroVAL and protonectin-F, were designed to reduce nonspecific toxicity and improve potency. Here, the three-dimensional structures of neuroVAL, protonectin and protonectin-F were determined by using circular dichroism and NMR spectroscopy. Antibacterial, antifungal, cytotoxic and hemolytic activities were tested for the parent peptides and analogues. All peptides showed moderate antimicrobial activity against Gram-positive bacteria, with agelaia-MPI being the most active. Protonectin and protonectin-F were found to be toxic to cancerous and noncancerous cell lines. Internalization experiments revealed that these peptides accumulate inside both cell types. By contrast, neuroVAL was nontoxic to all tested cells and was able to enter cells without accumulating. In summary, neuroVAL has potential as a nontoxic cell-penetrating peptide, while protonectin-F needs further modification to realize its potential as an antitumor peptide.     

Development of a new synthetic bone graft

A process for the replication of bovine cancellous bone in synthetic bioceramic materials for use as artificial bone graft substitutes is described. The process detailed here may be easily implemented to allow production of large numbers of blocks of material, even on a laboratory scale. The graft material has a pore morphology and interconnectivity identical with that of the original cancellous bone used as a starting material. Strength of the material is adequate, and at lower porosity levels it meets the FDA requirements for coralline materials for spinal applications. The synthetic graft is also shown to have excellent fluid-retention characteristics, making it a potential carrier for morphogenic agents such as solutions of bone morphogenic protein. © 1998 Kluwer Academic Publishers/p>     

Co-opting the Night: The Entrepreneurial Shift and Economic Imperative in NTE Planning

The City of Sydney Council has presented their night-time economy plan (NTE) – Open, Future directions for Sydney at night – as a unique and substantial contribution to global city planning literature. This paper critiques the plan and demonstrates how Open is strongly aligned with, and constrained by the neoliberal-inspired cultural-economy framework of the Council’s overarching policy vision: Sustainable Sydney 2030. Such co-opting of policy evinces an entrepreneurial shift in NTE planning where economic interests procure substantial voice in the consultation, and eventual policy directions of changing the nightscape. The paper explicates the economic imperative(s) of Open within the context of one inner city Sydney suburb, Surry Hills.     

High intensity compounding of mica-filled thermoplastics

High-speed turbine mixers have been adapted for compounding filled thermoplastics by the partial flux method. The extreme shearing forces exerted by the mixing impellors simultaneously mixes and delaminates mica fillers to form finely dispersed compounds in a granular, partially fused state which can be directly injection molded without pelletizing. In practice, one turbine mixing unit can be employed for compounding all types of resins and fillers. The partial flux method permits compounding to be accomplished at peak sensor temperatures that are considerably below the resin softening or melting transitions, frequently 50°C less than normal compounding temperatures. The short residence times and reduced energy requirements possible with partial fluxing results in substantial cost reduction without compromising quality or performance. Examples are provided for polypropylene, nylon 66, poly(butene terephthalate), poly(ethylene terephthalate) and poly(phenylene oxide) alloys. Impact modifiers derived from carboxylated polyolefin waxes may be dispersed by the intense shearing action to form highly subdivided submicron particles, which promote crazing and shear deformation during fracture testing, thereby contributing to increased composited toughness with minor sacrifice in modulus and strength. The mechanical properties of micafilled thermoplastics have also been compared with those of short glass fiber composites. In certain applications requiring stiffness and dimensional stability at elevated temperatures, mica composites prepared by intensive mixing in a turbine mixer may be economically substituted for glass fiber counterparts.     

Praticle Size Reduction in the Ball Mill

The size distribution produced by the ball milling of various crystalline and non-crystalline materials, showed that initially there was a fairly even distribution over the size range up to 355μm. However, as milling proceeded two distribution modes developed; one at about 90μm (the persistent mode) and one at about 250μm (the transitory mode). Unlike the work of Heywood (1) on coal, further grinding did not produce a gradual elimination of the coarse mode with corresponding increase in the persistent mode at 90μm. Less than 2%w/w of material was always found between the 170-180μm size, indicating that this was a critical dimension in the grinding process. A linear relationship was found between sample weight and milling time required to grind 50% of the sample down to 150μm. The slopes of these lines were steep for rock salt and sucrose (crystalline materials) indicating that milling was rapid, whilst with acacia the rate was half as fast and slower still for the other two non-crystalline materials, cinnamon bark and gentian root. In terms of milling efficiency defined as the amount of material milled to 150μm per minute, it was found that there was no optimum load size; doubling the sample size effectively doubled the milling time. However, the most critical factor affecting the milling process, was the weight and nature of the grinding medium. It was found that heavy porcelain was more efficient than glass spheres and that the optimum weight was 401.8g; the weight required to approximately half fill the ball mill.     

Quantification of solute-solute interactions using negligible-depletion solid-phase microextraction: measuring the affinity of estradiol to bulk organic matter

The interaction of trace organic contaminants with bulk organic matter has implications for the transport and behavior of organic trace contaminants within the aquatic environment as well as water and wastewater treatment processes. Partition coefficients (K(OM)) of the steroidal trace organic contaminant estradiol were quantified for environmentally relevant concentrations of bulk organic matter (12.5 mg C/L) using a full mass balance form of solid-phase microextraction (SPME). The results indicated that the method is successful and can be used at environmental concentrations. Estradiol had the greatest affinity for bulk organic matter that contained phenolic and benzoic acid ester groups, namely tannic acid, compared to organics containing predominately carboxylic functional groups. The solution chemistry (pH) was found to influence the interaction, as estradiol had a lower affinity for negatively charged and hydrophilic bulk organic matter. The partition coefficients determined using SPMEwere consistentwith partition coefficients derived using solubility enhancement and fluorescence quenching measurements, confirming that SPME is a powerful technique to quantify the affinity of estradiol for low concentrations of bulk organic matter and trace contaminants. Further, this novel method can be applied to a range of trace contaminants.