Porphyrins with metal, metalloid or phosphorus atoms directly bonded to the carbon periphery

Organometallic porphyrins with a metal, metalloid or phosphorus fragment directly attached to their carbon framework emerged for the first time in 1976, and these macrocycles have been intensively investigated in the past decade. The present review summarises for the first time all reported examples as well as applications of these systems.

Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

Nitrogen and phosphorus transformations in fixed-film biofilters subjected to aeration/no-aeration cycles

Despite recent developments in fixed-film combined biological nutrients removal (BNR) technology; fixed-film systems (i.e., biofilters), are still at the early stages of development and their application has been limited to a few laboratory-scale experiments. Achieving enhanced biological phosphorus removal in fixed-film systems requires exposing the micro-organisms and the waste stream to alternating anaerobic/aerobic or anaerobic/anoxic conditions in cycles. The concept of cycle duration (CD) as a process control parameter is unique to fixed-film BNR systems, has not been previously investigated, and can be used to optimise the performance of such systems. The CD refers to the elapsed time before the biomass is re-exposed to the same environmental conditions in cycles. Fixed-film systems offer many advantages over suspended growth systems such as reduced operating costs, simplicity of operation, absence of sludge recycling problems, and compactness. The control of nutrient discharges to water bodies, improves water quality, fish production, and allow water reuse. The main objective of this study was to develop a fundamental understanding of the effect of CD on the transformations of nutrients in fixed-film biofilter systems subjected to alternating aeration I no-aeration cycles A fixed-film biofilter system consisting of three up-flow biofilters connected in series was developed and tested. The first and third biofilters were operated in a cyclic mode in which the biomass was subjected to aeration/no-aeration cycles. The influent wastewater was simulated aquaculture whose composition was based on actual water quality parameters of aquacuture wastewater from a prawn grow-out facility. The influent contained 8.5 - 9:3 mg!L a111monia-N, 8.5- 8.7 mg/L phosphate-P, and 45- 50 mg!L acetate. Two independent studies were conducted at two biofiltration rates to evaluate and confirm the effect of CD on nutrient transformations in the biofilter system for application in aquaculture: A third study was conducted to enhance denitrification in the system using an external carbon- source at a rate varying from 0-24 ml/min. The CD was varied in the range of0.25- 120 hours for the first two studies and fixed at 12 hours for the third study. This study identified the CD as an important process control parameter that can be used to optimise the performance of full-scale fixed-film systems for BNR which represents a novel contribution in this field of research. The CD resulted in environmental conditions that inhibited or enhanced nutrient transformations. The effect of CD on BNR in fixed-film systems in terms of phosphorus biomass saturation and depletion has been established. Short CDs did not permit the establishment of anaerobic activity in the un-aerated biofilter and, thus, inhibited phosphorus release. Long CDs resulted in extended anaerobic activity and, thus, resulted in active phosphorus release. Long CDs, however, resulted in depleting the biomass phosphorus reservoir in the releasing biofilter and saturating the biomass phosphorus reservoir in the up-taking biofilter in the cycle. This phosphorus biomass saturation/depletion phenomenon imposes a practical limit on how short or long the CD can be. The length of the CD should be somewhere just before saturation or depletion occur and for the system tested, the optimal CD was 12 hours for the biofiltration rates tested. The system achieved limited net phosphorus removal due to the limited sludge wasting and lack of external carbon supply during phosphorus uptake. The phosphorus saturation and depletion reflected the need to extract phosphorus from the phosphorus-rich micro-organisms, for example, through back-washing. The major challenges of achieving phosphorus removal in the system included: (I) overcoming the deterioration in the performance of the system during the transition period following the start of each new cycle; and (2) wasting excess phosphorus-saturated biomass following the aeration cycle. Denitrification occurred in poorly aerated sections of the third biofilter and generally declined as the CD increased and as the time progressed in the individual cycle. Denitrification and phosphorus uptake were supplied by an internal organic carbon source, and the addition of an external carbon source (acetate) to the third biofilter resulted in improved denitrification efficiency in the system from 18.4 without supplemental carbon to 88.7% when the carbon dose reached 24 mL/min The removal of TOC and nitrification improved as the CD increased, as a result of the reduction in the frequency of transition periods between the cycles. A conceptual design of an effective fixed-film BNR biofilter system for the treatment of the influent simulated aquaculture wastewater was proposed based on the findings of the study.