Ana Soares

Nonylphenol in the environment : A critical review on occurrence, fate, toxicity and treatment in wastewaters

Nonylphenol is a toxic xenobiotic compound classified as an endocrine disrupter capable of interfering with the hormonal system of numerous organisms. It originates principally from the degradation of nonylphenol ethoxylates which are widely used as industrial surfactants. Nonylphenol ethoxylates reach sewage treatment works in substantial quantities where they biodegrade into several by-products including nonylphenol. Due to its physical-chemical characteristics, such as low solubility and high hydrophobicity, nonylphenol accumulates in environmental compartments that are characterised by high organic content, typically sewage sludge and river sediments, where it persists. The occurrence of nonylphenol in the environment is clearly correlated with anthropogenic activities such as wastewater treatment, landfilling and sewage sludge recycling. Nonylphenol is found often in matrices such as sewage sludge, effluents from sewage treatment works, river water and sediments, soil and groundwater. The impacts of nonylphenol in the environment include feminization of aquatic organisms, decrease in male fertility and the survival of juveniles at concentrations as low as 8.2 microg/l. Due to the harmful effects of the degradation products of nonylphenol ethoxylates in the environment, the use and production of such compounds have been banned in EU countries and strictly monitored in many other countries such as Canada and Japan. Although it has been shown that the concentration of nonylphenol in the environment is decreasing, it is still found at concentrations of 4.1 microg/l in river waters and 1 mg/kg in sediments. Nonylphenol has been referred to in the list of priority substances in the Water Frame Directive and in the 3rd draft Working Document on Sludge of the EU. Consequently there is currently a concern within some industries about the possibility of future regulations that may impose the removal of trace contaminants from contaminated effluents. The significance of upgrading sewage treatment works with advanced treatment technologies for removal of trace contaminants is discussed.

Comparison between disintegrated and fermented sewage sludge for production of a carbon source suitable for biological nutrient removal

There is a need to investigate processes that enable sludge re-use while enhancing sewage treatment efficiency. Mechanically disintegrated thickened surplus activated sludge (SAS) and fermented primary sludge were compared for their capacity to produce a carbon source suitable for BNR by completing nutrient removal predictive tests. Mechanically disintegration of SAS using a deflaker enhanced volatile fatty acids (VFAs) content from 92 to 374 mg l(-1) (4.1-fold increase). In comparison, primary sludge fermentation increased the VFAs content from 3.5 g l(-1) to a final concentration of 8.7 g l(-1) (2.5-fold increase). The carbon source obtained from disintegration and fermentation treatments improved phosphate (PO(4)-P) release and denitrification by up to 0.04 mg NO(3)-Ng(-1)VSS min(-1) and 0.031 mg PO(4)-Pg(-1)VSS min(-1), respectively, in comparison to acetate (0.023 mg NO(3)-Ng(-1)VSS min(-1)and 0.010 mg PO(4)-Pg(-1)VSS min(-1)). Overall, both types of sludge were suitable for BNR but disintegrated SAS displayed lower carbon to nutrient ratios of 8 for SCOD:PO(4)-P and 9 for SCOD:NO(3)-N. On the other hand, SAS increased the concentration of PO(4)-P in the settled sewage by a further 0.97 g PO(4)-P kg(-1)SCOD indicating its potential negative impact towards nutrient recycling in the BNR process.

Gap junctional protein Cx43 is involved in the communication between extracellular vesicles and mammalian cells

Intercellular communication is vital to ensure tissue and organism homeostasis and can occur directly, between neighbour cells via gap junctions (GJ), or indirectly, at longer distances, through extracellular vesicles, including exosomes. Exosomes, as intercellular carriers of messenger molecules, mediate the transfer of biological information between donor and acceptor cells. Although the biological effects of exosomes in target cells have been intensively studied, the mechanisms that govern exosomal uptake are not fully understood. Here, we show that Connexin 43 (Cx43), the most widely expressed GJ protein, is present in exosomes in the form of hexameric channels and, more importantly, that exosomal Cx43 is able to modulate the interaction and transfer of information between exosomes and acceptor cells. This study envisions a new paradigm where Cx43-containing channels mediate the release of exosomal content into cells, which constitutes a novel and unanticipated mechanism to modulate intercellular communication.

The effectiveness of anaerobic digestion in removing estrogens and nonylphenol ethoxylates.

The fate and behaviour of two groups of endocrine disrupting chemicals, steroid estrogens and nonylphenol ethoxylates, have been evaluated during the anaerobic digestion of primary and mixed sewage sludge under mesophilic and thermophilic conditions. Digestion occurred over six retention times, in laboratory scale reactors, treating sludges collected from a sewage treatment works in the United Kingdom. It has been established that sludge concentrations of both groups of compounds demonstrated temporal variations and that concentrations in mixed sludge were influenced by the presence of waste activated sludge as a result of transformations during aerobic treatment. The biodegradation of total steroid estrogens was >50% during primary sludge digestion with lower removals observed for mixed sludge, which reflected bulk organic solids removal efficiencies. The removal of nonylphenol ethoxylates was greater in mixed sludge digestion (>58%) compared with primary sludge digestion and did not reflect bulk organic removal efficiencies. It is apparent that anaerobic digestion reduces the concentrations of these compounds, and would therefore be expected to confer a degree of protection against exposure and transfer of both groups of compounds to the receiving/re-use environment.

Biologically and chemically mediated adsorption and precipitation of phosphorus from wastewater

Biologically and chemically mediated adsorption and precipitation processes offer a range of approaches for removing phosphorus (P) from agricultural, domestic and industrial effluents. Technologies implemented at full-scale include filtration by adsorbent media, such as steel slag, and recovery of phosphorus as struvite, which has been successfully commercialised as a fertiliser. Other promising technologies under investigation include P removal by polymers and nanomaterials as well as struvite formation by bacteria. There is a need to focus future research on improving the efficiency of P removal by adsorption and precipitation. This can be achieved by techniques such as regenerating filters, polymers and nanomaterials for renewed P removal. Research is also needed to optimise the fertiliser potential of struvite precipitates.

An internal carbon source for improving biological nutrient removal.

This study investigates the potential of mechanically disintegrated surplus activated sludge (SAS) to be used as an internal carbon source for biological nutrient removal (BNR) using two laboratory tests. In the phosphorus release test, the addition of disintegrated sludge as a carbon source was able to enhance phosphate (PO(4)-P) release by 14.9 mg l(-1) PO(4)-P when compared with acetate (7.9 mg l(-1) PO(4)-P), considering the 4.3 mg l(-1) PO(4)-P released in the control vessel, without carbon addition. Similarly, in the denitrification test, the nitrate (NO(3)-N) consumption rate was improved after the addition of disintegrated sludge (14.9 mg NO(3)-Ng(-1)VSS h(-1)) compared with acetate (7.0 mg NO(3)-Ng(-1)VSS h(-1)), taking in consideration the rate obtained in the control vessel (6.9 mg NO(3)-Ng(-1)VSS h(-1)). Two to five minutes of SAS disintegration time in the deflaker (2300-6200 kJ kg(-1) total solids) is recommended for this application.

Preliminary evaluation of new polymer matrix for solid-phase extraction of nonylphenol from water samples.

Molecularly imprinted (MIP) and blank polymers with affinity for nonylphenol were designed using computational modelling. Chromatographic tests demonstrated higher affinity of imprinted polymers towards the template nonylphenol as compared with blank polymers. The performance of both polymers in solid-phase extraction was however very similar. Both blank and imprinted polymers appeared to be suitable for the removal and pre-concentration of nonylphenol from contaminated water samples with 99% efficiency of the recovery. The commercial resins PH(EC) (Biotage) and C18 (Varian) tested in the same conditions used for comparative purposes had recovery rate <84%. The polymer capacity for nonylphenol was 231 mg g(-1) for blank and 228 mg g(-1) for MIP. The synthesised materials can have significance for sample pre-concentration and environmental analysis of this class of compounds.

Fate of Alkylphenolic Compounds during Activated Sludge Treatment: Impact of Loading and Organic Composition

The impact of loading and organic composition on the fate of alkylphenolic compounds in the activated sludge plant (ASP) has been studied. Three ASP designs comprising carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification treatment were examined to demonstrate the impact of increasing levels of process complexity and to incorporate a spectrum of loading conditions. Based on mass balance, overall biodegradation efficiencies for nonylphenol ethoxylates (NPEOs), short chain carboxylates (NP(1-3)EC) and nonylphenol (NP) were 37%, 59%, and 27% for the carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification ASP, respectively. The presence of a rich community of ammonia oxidizing bacteria does not necessarily facilitate effective alkylphenolic compound degradation. However, a clear correlation between alkylphenolic compound loading and long chain ethoxylate compound biodegradation was determined at the three ASPs, indicating that at higher initial alkylphenolic compound concentrations (or load), greater ethoxylate biotransformation can occur. In addition, the impact of settled sewage organic composition on alkylphenolic compound removal was evaluated. A correlation between the ratio of chemical oxygen demand (COD) to alkylphenolic compound concentration and biomass activity was determined, demonstrating the inhibiting effect of bulk organic matter on alkylphenol polyethoxylate transformation activity. At all three ASPs the biodegradation pathway proposed involves the preferential biodegradation of the amphiphilic ethoxylated compounds, after which the preferential attack of the lipophilic akylphenol moiety occurs. The extent of ethoxylate biodegradation is driven by the initial alkylphenolic compound concentration and the proportion of COD constituted by the alkylphenol polyethoxylates (APEOs) and their metabolites relative to the bulk organic concentration of the sewage composed of proteins, acids, fats, and polysaccharides. Secondary effluents from this study are characterized by low bulk organic concentrations and comparatively high micropollutant concentrations. Based on the biodegradation mechanism proposed in this study, application of high rate tertiary biological treatment processes to secondary effluents characterized by low bulk organic concentrations and comparatively high APEO concentrations is predicted to provide a sustainable solution to micropollutant removal.

Carbon capture and biogas enhancement by carbon dioxide enrichment of anaerobic digesters treating sewage sludge or food waste.

The increasing concentration of carbon dioxide (CO2) in the atmosphere and the stringent greenhouse gases (GHG) reduction targets, require the development of CO2 sequestration technologies applicable for the waste and wastewater sector. This study addressed the reduction of CO2 emissions and enhancement of biogas production associated with CO2 enrichment of anaerobic digesters (ADs). The benefits of CO2 enrichment were examined by injecting CO2 at 0, 0.3, 0.6 and 0.9 M fractions into batch ADs treating food waste or sewage sludge. Daily specific methane (CH4) production increased 11-16% for food waste and 96-138% for sewage sludge over the first 24h. Potential CO2 reductions of 8-34% for sewage sludge and 3-11% for food waste were estimated. The capacity of ADs to utilise additional CO2 was demonstrated, which could provide a potential solution for onsite sequestration of CO2 streams while enhancing renewable energy production.

K63 linked ubiquitin chain formation is a signal for HIF1A degradation by Chaperone-Mediated Autophagy

Chaperone-Mediated Autophagy is a selective form of autophagy. Recently, the degradation of a newly identified CMA substrate, the HIF1A transcription factor, was found to be regulated by the ubiquitin ligase STUB1. In this study we show, for the first time, that K63 ubiquitination is necessary for CMA degradation of HIF1A in vitro and in vivo. Additionally, STUB1 mediates K63 linked ubiquitination of HIF1A. Our findings add a new regulatory step and increase the specificity of the molecular mechanism involved in CMA degradation of HIF1A, expanding the role of ubiquitination to yet another biological process, since the same mechanism might be applicable to other CMA substrates.