Assessment of biotechnological strategies for the valorization of metal bearing wastes

The present work deals with the application of biotechnology for the mobilization of metals from different solid wastes: end of life industrial catalysts, heavy metal contaminated marine sediments and fluorescent powders coming from a cathode ray tube glass recycling process. Performed experiments were aimed at assessing the performance of acidophilic chemoautotrophic Fe/S-oxidizing bacteria for such different solid matrices, also focusing on the effect of solid concentration and of different substrata. The achieved results have evidenced that metal solubilization seems to be strongly influenced by the metal speciation and partitioning in the solid matrix. No biological effect was observed for Ni, Zn, As, Cr mobilization from marine sediments (34%, 44%, 15%, 10% yields, respectively) due to metal partitioning. On the other hand, for spent refinery catalysts (Ni, V, Mo extractions of 83%, 90% and 40%, respectively) and fluorescent powders (Zn and Y extraction of 55% and 70%, respectively), the improvement in metal extraction observed in the presence of a microbial activity confirms the key role of Fe/S oxidizing bacteria and ferrous iron. A negative effect of solid concentration was in general observed on bioleaching performances, due to the toxicity of dissolved metals and/or to the solid organic component.     

Retaining natural vegetation to safeguard biodiversity and humanity

Global efforts to deliver internationally agreed goals to reduce carbon emissions, halt biodiversity loss, and retain essential ecosystem services have been poorly integrated. These goals rely in part on preserving natural (e.g., native, largely unmodified) and seminatural (e.g., low intensity or sustainable human use) forests, woodlands, and grasslands. To show how to unify these goals, we empirically derived spatially explicit, quantitative, area-based targets for the retention of natural and seminatural (e.g., native) terrestrial vegetation worldwide. We used a 250-m-resolution map of natural and seminatural vegetation cover and, from this, selected areas identified under different international agreements as being important for achieving global biodiversity, carbon, soil, and water targets. At least 67 million km² of Earth's terrestrial vegetation (∼79% of the area of vegetation remaining) required retention to contribute to biodiversity, climate, soil, and freshwater conservation objectives under 4 United Nations’ resolutions. This equates to retaining natural and seminatural vegetation across at least 50% of the total terrestrial (excluding Antarctica) surface of Earth. Retention efforts could contribute to multiple goals simultaneously, especially where natural and seminatural vegetation can be managed to achieve cobenefits for biodiversity, carbon storage, and ecosystem service provision. Such management can and should co-occur and be driven by people who live in and rely on places where natural and sustainably managed vegetation remains in situ and must be complemented by restoration and appropriate management of more human-modified environments if global goals are to be realized.     

Identifying hydrologically sensitive areas: bridging the gap between science and application

Researchers have noted that current water quality protection strategies, like nutrient management plans, lack a sound hydrological underpinning for pollutant transport processes. This is especially true for areas like the northeastern U.S. where copious research has shown that variable source area hydrology largely governs runoff generation. The goal of this study was to develop a scientifically justified method to identify the locations that generate overland flow. Furthermore, this methodology must be computationally simple enough that it can be utilized or incorporated into nutrient management plans and other established water quality tools. We specifically tested the reliability of the 'distance from a stream,'D(s), and the 'topographic index,'lambda, to predict areas with a high propensity for generating overland flow, i.e. hydrologically sensitive areas (HSA). HSAs were defined by their probability of generating runoff, P(sat), based on 30 year simulations using a physically based hydrological model. Using GIS, each location's P(sat) was correlated with D(s) and lambda. We used three Delaware Co., NY watersheds in the New York City watershed system with areas varying in size from 1.6 to 37 km2 and with forested and agricultural land uses. The topographic index gave stronger, more regionally consistent correlations with P(sat) than did D(s). Equations correlating lambda and P(sat) for each month are presented and can be used to estimate hydrological sensitivity in the region surrounding our study watersheds, i.e. in Delaware Co. This work is currently being incorporated into an Internet Mapping System to facilitate user-friendly, on-line identification of HSAs.     

Efforts to Reduce Mortality to Hydroelectric Turbine-Passed Fish: Locating and Quantifying Damaging Shear Stresses

Severe fluid forces are believed to be a source of injury and mortality to fish that pass through hydroelectric turbines. A process is described by which laboratory bioassays, computational fluid dynamics models, and field studies can be integrated to evaluate the significance of fluid shear stresses that occur in a turbine. Areas containing potentially lethal shear stresses were identified near the stay vanes and wicket gates, runner, and in the draft tube of a large Kaplan turbine. However, under typical operating conditions, computational models estimated that these dangerous areas comprise less than 2% of the flow path through the modeled turbine. The predicted volumes of the damaging shear stress zones did not correlate well with observed fish mortality at a field installation of this turbine, which ranged from less than 1% to nearly 12%. Possible reasons for the poor correlation are discussed. Computational modeling is necessary to develop an understanding of the role of particular fish injury mechanisms, to compare their effects with those of other sources of injury, and to minimize the trial and error previously needed to mitigate those effects. The process we describe is being used to modify the design of hydroelectric turbines to improve fish passage survival.     

Effective Transboundary Aquifer Areas: An Approach for Transboundary Groundwater Management

The natural complexity, heterogeneity, and extent of transboundary aquifers around the world, have led to controversy over which method or criteria should be used to identify and delineate their boundaries. Currently, there is no standard methodology that aquifer‐sharing countries can use to delineate the area of a transboundary aquifer. In the case of Mexico and Texas, Mexico uses administrative boundaries, whereas Texas uses geological boundaries. This paper proposes a method for delineation and prioritization of aquifers (or aquifer areas) called effective transboundary aquifer areas (ETAAs), which uses a combination of physical criteria (geological boundaries, topography, and hydrography) and the location and density of active water wells in the borderland between Mexico and Texas. This method identifies the area of priority (productivity area) in the aquifer using pumping patterns or hot spots regardless of the aquifer’s surficial geological limits, therefore offering a more effective, local and practical management option at the transboundary level. Different geological features or pumping patterns will have different sizes and locations of ETAAs within the same aquifer. In West Texas, which is dominated by bolsons, the method produces limited options for ETAAs, whereas in South Texas in the easternmost border the identified ETAAs are more significant.     

The net ecosystem carbon exchange of human-modified environments in the Australian Capital Region

As part of a larger study to quantify and map ecosystem services in southeast Australia, we estimated carbon stored in biomass and soils and the net ecosystem carbon exchange between the land surface and the atmosphere in the Australian Capital Region (ACR). Our aim was to understand and quantify how different human-modified landscapes provide an essential ecosystem service: the exchange and storage of carbon in the landscape. Using a remote sensing based modelling methodology, we obtained values of Net Primary Productivity (NPP), total carbon in soil and biomass and carbon turnover from meteorological and terrain inputs and vegetation attributes. We obtained a set of maps of NPP, total carbon (C) storage and C-turnover for the ACR. We superimposed a land use/cover map to assign the uptake, storage and release of carbon to different land use/cover types. Our results support the hypothesis that human-intensive land uses significantly affect the ability of terrestrial ecosystems to provide an important ecosystem service in the form of carbon storage.     

Phytoestrogens and mycotoxins in Iowa streams: an examination of underinvestigated compounds in agricultural basins

This study provides the first broad-scale investigation on the spatial and temporal occurrence of phytoestrogens and mycotoxins in streams in the United States. Fifteen stream sites across Iowa were sampled five times throughout the 2008 growing season to capture a range of climatic and crop-growth conditions. Basin size upstream from sampling sites ranged from 7 km2 to > 836,000 km2. Atrazine (herbicide) also was measured in all samples as a frame-of-reference agriculturally derived contaminant. Target compounds were frequently detected in stream samples: atrazine (100%), formononetin (80%), equol (45%), deoxynivalenol (43%), daidzein (32%), biochanin A (23%), zearalenone (13%), and genistein (11%). The nearly ubiquitous detection of formononetin (isoflavone) suggests a widespread agricultural source, as one would expect with the intense row crop and livestock production present across Iowa. Conversely, the less spatially widespread detections of deoxynivalenol (mycotoxin) suggest a more variable source due to the required combination of proper host and proper temperature and moisture conditions necessary to promote Fusarium spp. infections. Although atrazine concentrations commonly exceeded 100 ng L(-1) (42/75 measurements), only deoxynivalenol (6/56 measurements) had concentrations that occasionally exceeded this level. Temporal patterns in concentrations varied substantially between atrazine, formononetin, and deoxynivalenol, as one would expect for contaminants with different source inputs and processes of formation and degradation. The greatest phytoestrogen and mycotoxin concentrations were observed during spring snowmelt conditions. Phytoestrogens and mycotoxins were detected at all sampling sites regardless of basin size. The ecotoxicological effects from long-term, low-level exposures to phytoestrogens and mycotoxins or complex chemicals mixtures including these compounds that commonly rake place in surface water are poorly understood and have yet to be systematically investigated in environmental studies.     

A Simple Framework for Incorporating Seasonal Streamflow Forecasts into Existing Water Resource Management Practices1

Gong, Gavin, Lucien Wang, Laura Condon, Alastair Shearman, and Upmanu Lall, 2010. A Simple Framework for Incorporating Seasonal Streamflow Forecasts Into Existing Water Resource Management Practices. Journal of the American Water Resources Association (JAWRA) 46(3):574-585. DOI: 10.1111/j.1752-1688.2010.00435.x Abstract: Climate-based streamflow forecasting, coupled with an adaptive reservoir operation policy, can potentially improve decisions by water suppliers and watershed stakeholders. However, water suppliers are often wary of straying too far from their current management practices, and prefer forecasts that can be incorporated into existing system modeling tools. This paper presents a simple framework for utilizing streamflow forecasts that works within an existing management structure. Climate predictors are used to develop seasonal inflow forecasts. These are used to specify operating rules that connect to the probability of future (end of season) reservoir states, rather than to the current storage, as is done now. By considering both current storage and anticipated inflow, the likelihood of meeting management goals can be improved. The upper Delaware River Basin in the northeastern United States is used to demonstrate the basic idea. Physically plausible climate-based forecasts of March-April reservoir inflow are developed. Existing simulation tools and rule curves for the system are used to convert the inflow forecasts to reservoir level forecasts. Operating policies are revised during the forecast period to release less water during forecasts of low reservoir level. Hindcast simulations demonstrate reductions of 1.6% in the number of drought emergency days, which is a key performance measure. Forecasts with different levels of skill are examined to explore their utility.     

Oxidative degradation of chlorophenol derivatives promoted by microwaves or power ultrasound: a mechanism investigation

Background, aim, and scope

Phenols are the most common pollutants in industrial wastewaters (particularly from oil refineries, resin manufacture, and coal processing). In the last two decades, it has become common knowledge that they can be effectively destroyed by nonconventional techniques such as power ultrasound (US) and/or microwave (MW) irradiation. Both techniques may strongly promote advanced oxidation processes (AOPs). The present study aimed to shed light on the effect and mechanism of US- and MW-promoted oxidative degradation of chlorophenols; 2,4-dichlorophenoxyacetic acid (2,4-D), a pesticide widespread in the environment, was chosen as the model compound.

Materials and methods

2,4-D degradation by AOPs was carried out either under US (20 and 300 kHz) in aqueous solutions (with and without the addition of Fenton reagent) or solvent-free under MW with sodium percarbonate (SPC). All these reactions were monitored by gas chromatography–mass spectrometry (GC–MS) analysis and compared with the classical Fenton reaction in water under magnetic stirring. The same set of treatments was also applied to 2,4-dichlorophenol (2,4-DCP) and phenol, the first two products that occur a step down in the degradation sequence. Fenton and Fenton-like reagents were employed at the lowest active concentration.

Results

The effects of US and MW irradiation were investigated and compared with those of conventional treatments. Detailed mechanisms of Fenton-type reactions were suggested for 2,4-D, 2,4-DCP, and phenol, underlining the principal degradation products identified. MW-promoted degradation under solvent-free conditions with solid Fenton-like reagents (viz. SPC) is extremely efficient and mainly follows pyrolytic pathways. Power US strongly accelerates the degradation of 2,4-D in water through a rapid generation of highly reactive radicals; it does not lead to the formation of more toxic dimers.

Discussion

We show that US and MW enhance the oxidative degradation of 2,4-D and that a considerable saving of oxidants and cutting down of reaction times is thereby achieved. The results support the interpretation of previously published data and improve the understanding of the factors of direct degradation along different pathways.

Conclusions

Oxidative pathways for 2,4-D, 2,4-DCP, and phenol were proposed by a careful monitoring of the reactions and detection of intermediates by GC–MS.

Recommendations and perspectives

The understanding of the factors that affect chlorophenols degradation along different pathways may facilitate the optimization of the treatment. Type of energy source (US or MW), power, and frequency to be applied could be designed in function of the operative scenario (amount of pollutant in soil, water, or oils).     

Nocturnal NO3 radical chemistry in Houston,TX

Radical chemistry in the nocturnal urban boundary layer is dominated by the nitrate radical, NO₃, which oxidizes hydrocarbons and, through the aerosol uptake of N₂O₅, indirectly influences the nitrogen budget. The impact of NO₃ chemistry on polluted atmospheres and urban air quality is, however, not well understood, due to a lack of observations and the strong impact of vertical stability of the boundary layer, which makes nocturnal chemistry highly altitude dependent.Here we present long-path DOAS observations of the vertical distribution of the key nocturnal species O₃, NO₂, and NO₃ during the TRAMP experiment in Summer 2006 in Houston, TX. Our observations confirm the altitude dependence of nocturnal chemistry, which is reflected in the concentration profiles of all trace gases at night. In contrast to other study locations, NO₃ chemistry in Houston is dominated by industrial emissions of alkenes, in particular of isoprene, isobutene, and sporadically 1,3-butadiene, which are responsible for more than 70% of the nocturnal NO₃ loss. The nocturnally averaged loss of NO_x in the lowest 300 m of the Houston atmosphere is ～0.9 ppb h^?1, with little day-to-day variability. A comparison with the daytime NO_x loss shows that NO₃ chemistry is responsible for 16–50% of the NO_x loss in a 24-h period in the lowest 300 m of the atmosphere. The importance of the NO₃ + isoprene/1,3-butadiene reactions implies the efficient formation of organic nitrates and secondary organic aerosol at night in Houston.