Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

Horizontal mergers in the iron ore industry—An application of PCAIDS

The purpose of this paper is to estimate and analyse the price effects of the iron ore mergers between Rio Tinto and North Ltd in 2000, and CVRD and Caemi in 2001. The analyses are conducted using a merger simulation model that, based on the pre-merger situation, estimates the post-merger outcome. This paper applies the so-called proportionality-calibrated almost ideal demand system (PCAIDS) model, which assumes that the product is differentiated and that the strategic variable is price. The results from the merger simulations show that in the case of the merger between Rio Tinto and North Ltd, the merged firm has a combined market share of almost 20%. However, the estimated market weighted average price effect is only 2.6%. Regarding the merger between CVRD and Caemi, the merged firm's market share is about 29%, and the estimated market weighted average price effect is 4.6%. When removing Caemi's Canadian asset, which was the Commission decision in order to allow the merger, the market price effect decreases to 3.1%. Overall the results in this study support the Commission's decisions regarding both merger cases, and shows that merger simulations of price effects can be valuable tools in merger assessments.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Metal concentrations in American oyster <Emphasis Type="Italic">Crassotrea virginica</Emphasis> and adjacent sediments from harvestable and non-harvestable sites in the Southeastern USA

Human population growth in coastal areas continues to threaten estuarine ecosystems and resources. Populations of Crassostrea virginica have declined across the USA due to water quality degradation, disease pressure, alteration of habitat, and other changes related to anthropogenic impacts. Metals that may be present in estuarine habitats can bioaccumulate in oysters, with potential consequences to the health of oysters and humans consumers. This study (1) evaluated the occurrence and relationships of metal concentrations in oyster tissue versus estuarine sediments, (2) examined oyster tissue concentrations in relation to state water quality designations, and (3) evaluated the potential risk for humans from oyster consumption related to metal concentrations from harvestable waters. Results indicated metal concentrations in sediments and oysters along coastal South Carolina remain low compared to other areas and that concentrations in oyster tissue and adjacent sediments were not highly correlated with each other. However, high concentrations of some metals occurred in oysters sampled from areas designated as Approved for Harvesting. This is important because most harvest area designation systems rely on regular bacterial monitoring when evaluating the safety of consumption. Others safety measurements may be necessary as part of routine monitoring.     

A survey on the utility of the USEPA CADDIS stressor identification procedure

The Environmental Protection Agency (EPA) has made available on the worldwide web a systematic stream stressor identification procedure, the “Causal Analysis/Diagnosis Decision Information System” or CADDIS. We report here the results of a survey of regulators and scientists in 11 states who use CADDIS or another stressor identification procedure in their work. The 13 survey questions address guidelines as to what impairment scenarios to approach with stressor identification, what information is needed to perform stressor identification, and what the stakeholder role is in performing stressor identification. At the time of this survey (the summer of 2009), the EPA CADDIS website was less commonly used among the state regulators surveyed than the published EPA stressor identification document on which it is based. The respondents generally find the EPA stressor identification procedure useful and capable of being adapted to their individual needs. Survey respondents all use stressor identification in their Total Maximum Daily Load work, but also in a wide variety of other applications. All the “types of evidence” included in the CADDIS stressor identification procedure are used by the practitioners surveyed with the exception of the results of ecological simulation models. While the CADDIS documentation encourages the involvement of stakeholders in stressor identification, most respondents do not assemble stakeholder teams of local officials and citizens to participate in stressor analyses.     

Biopolymer (Chitin) from Various Marine Seashell Wastes: Isolation and Characterization

Chitin has been produced from different sea waste sources including, molluscs (mussel and oyster shell), crustacean (prawn and crab) and fish scale (pang and silver scales) using deproteinization and demineralization as chemical methods. The conditions of chemical extraction process determine the quality of chitin. The obtained results revealed that, about 1 and 10% HCl and NaOH were adequate concentrations for deproteinization and demineralization process respectively. Chitin from oyster and crab shell waste had the highest yield of 69.65 and 60.00% while prawn, mussel shell, pang and silver scales had the lowest yield of 40.89, 35.03, 35.07 and 31.11% respectively. Chitin solubility is controlled by the quantity of protonated acetyl groups within the polymeric chain of the chitin backbone, thus on the percentage of acetylated and non-acetylated d-glucos-acetamide unit. Good solubility results were obtained in mussel, oyster and crab shells respectively. The chitin molecular weight characteristics and activity are controlled by the degree of acetylation (DA) and the distribution of acetyl group extending in the polymer chain. DA is determined by acid-base titration methods and molecular weight determined by Brookfield viscometry. Both methods are found to be effective.     

Photo-Stabilisation and UV Blocking Efficacy of Coated Macro and Nano-Rutile Titanium Dioxide Particles in Paints and Coatings

Surface treated macro and nanoparticle TiO₂ samples have been prepared, characterised and their efficiency as UV blockers evaluated in clear coatings and paints. The particle size of the ‘base’ TiO₂ has been optimised to block UV radiation and the surface treatment developed to deactivate the photocatalytic activity of the surface of the TiO₂ particles. The resultant UV blockers have been evaluated in both solvent and water-based clear coatings. Nanoparticle TiO₂ has been prepared from ‘seed’ and the particle size was controlled by calcination. It was found that the choice of particle size is a compromise between UVA absorption, UVB absorption, visible transmission and photoactivity. It has been demonstrated that TiO₂ with a crystallite size of 25 nm yields a product with the optimum properties. A range of dispersants was successfully used to disperse and mill the TiO₂. Both organic and inorganic dispersants were used; 2-amino-2-methyl-1-propanol and 1-amino-2-propanol (MIPA) and P₂O₅ and Na₂SiO₃ respectively. The surface of the nano-TiO₂ was coated with mixed oxides of silicon, aluminium, zirconium and phosphorous. Addition of the resultant coated nano-rutiles to an Isocyanate Acrylic clear coating prolonged the lifetime of that coating compared to the blank. Generally, a surface treatment based on SiO₂, Al₂O₃ and P₂O₅ was more successful than one based on ZrO₂, Al₂O₃ and P₂O₅. Higher addition levels of the surface treatment were beneficial for protecting the polymeric coating. The UV blocker products were also evaluated in a water-based acrylic, first a water-based dispersion of the UV blocker was prepared before addition to the acrylic. The dispersions and resultant acrylic thin films were evaluated using UV/Vis spectroscopy and durability assessed. The ratio of absorbance at 300:500 nm for the water-based dispersion was shown to be a good predictor of both the transparency of the resultant acrylic thin film and the durability of that film, in terms of weight loss. Macro grade titanium dioxide pigments were also prepared and coated with treatments of silica, alumina and siloxane and their photo-stabilising activity in alkyd paint film assessed and found to be directly related to the electron–hole pair mobility and trapping as determined by micro-wave spectroscopy.     

Are we planning for sustainable disaster recovery? Evaluating recovery plans after the Wenchuan earthquake

This article examines local recovery plans that were created in response to the Wenchuan earthquake and then suggests ways that planners can better apply the concept of sustainability to the recovery process. We utilize a plan evaluation protocol to analyze 16 recovery plans in counties and towns that were severely affected by the earthquake. We also conducted semi-structured interviews with public officials and planners, with the qualitative data gleaned from these interviews being used to supplement the plan quality assessment. The results reveal that local recovery plans do not appear to have incorporated sufficiently the concepts of sustainability. We conclude the paper with the following recommendations: emphasizing sustainability as a policy priority during vision and goal development; developing solid databases and planning techniques; designing a diversified set of regulatory- and incentive-based policy tools suitable for local governments; enhancing social and institutional learning; and further integrating multi-level and interagency governmental units.     

Comparative statistical study of hourly precipitation determined by radar-based Stage IV and ground-based methods in the North Central United States

Detailed hourly precipitation data are required for long-range modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants using the CALPUFF model. In sparsely populated areas such as the north central United States, ground-based precipitation measurement stations may be too widely spaced to offer a complete and accurate spatial representation of hourly precipitation within a modeling domain. The availability of remotely sensed precipitation data by satellite and the National Weather Service array of next-generation radars (NEXRAD) deployed nationally provide an opportunity to improve on the paucity of data for these areas. Before adopting a new method of precipitation estimation in a modeling protocol, it should be compared with the ground-based precipitation measurements, which are currently relied upon for modeling purposes. This paper presents a statistical comparison between hourly precipitation measurements for the years 2006 through 2008 at 25 ground-based stations in the north central United States and radar-based precipitation measurements available from the National Center for Environmental Predictions (NCEP) as Stage IV data at the nearest grid cell to each selected precipitation station. It was found that the statistical agreement between the two methods depends strongly on whether the ground-based hourly precipitation is measured to within 0.1 in/hr or to within 0.01 in/hr. The results of the statistical comparison indicate that it would be more accurate to use gridded Stage IV precipitation data in a gridded dispersion model for a long-range simulation, than to rely on precipitation data interpolated between widely scattered rain gauges.

Implications:

The current reliance on ground-based rain gauges for precipitation events and hourly data for modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants results in potentially large discontinuity in data coverage and the need to extrapolate data between monitoring stations. The use of radar-based precipitation data, which is available for the entire continental United States and nearby areas, would resolve these data gaps and provide a complete and accurate spatial representation of hourly precipitation within a large modeling domain.     

Evaluating anthropogenic N inputs to diverse lake basins: A case study of three Chinese lakes

The environmental degradation of lakes in China has become increasingly serious over the last 30 years and eutrophication resulting from enhanced nutrient inputs is considered a top threat. In this study, a quasi-mass balance method, net anthropogenic N inputs (NANI), was introduced to assess the human influence on N input into three typical Chinese lake basins. The resultant NANI exceeded 10 000 kg N km⁻² year⁻¹ for all three basins, and mineral fertilizers were generally the largest sources. However, rapid urbanization and shrinking agricultural production capability may significantly increase N inputs from food and feed imports. Higher percentages of NANI were observed to be exported at urban river outlets, suggesting the acceleration of NANI transfer to rivers by urbanization. Over the last decade, the N inputs have declined in the basins dominated by the fertilizer use but have increased in the basins dominated by the food and feed import. In the foreseeable future, urban areas may arise as new hotspots for nitrogen in China while fertilizer use may decline in importance in areas of high population density.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-015-0638-8) contains supplementary material, which is available to authorized users.