Copper availability assessment of Cu-contaminated vineyard soils using black oat cultivation and chemical extractants

Grapevines grown on acid soils with low fertility in southern Brazil are treated with intense foliar applications of copper (Cu) fungicides, resulting in an increased level of Cu in the soil and increased toxicity. The present study evaluated the accumulation and bioavailability of Cu, and soils with varying levels of Cu from the main producing regions of southern Brazil were collected. The forms of Cu present in the soil were assessed using chemical extractants; additionally, oat cultivation was performed, reflecting the use of the plant as an indicator of Cu bioavailability. Cu accumulated in the topsoil, mainly in bioavailable forms, and there was also an increase of Cu up to a depth of 0.4 m. Cu was primarily found in the mineral fraction, with apparent saturation of the soil organic matter functional groups. Inceptisol and Alfisol soils with a long history of cupric fungicide application were found to have levels of Cu toxic to oat plants. Furthermore, accumulated copper in Alfisol soil from the Campanha Gaúcha region of the state of Rio Grande do Sul had higher bioavailability compared to Cu accumulated in Inceptisol soil from the Serra Gaúcha region. In addition, the copper concentration in roots was found to serve as an indicator of Cu bioavailability in soil, but not of copper phytotoxicity in plants.     

A review on human attitudes towards reptiles in Brazil

For many millennia humans and reptiles have interacted, but the attitude of humans towards these animals has depended on culture, environment, and personal experience. At least 719 reptile species are known to occur in Brazil and about 11% of this fauna has been exploited for many different purposes, including bushmeat, leather, ornamental and magic/religious uses, and as folk medicines. Brazil can therefore serve as an interesting case study for better understanding reptile use by human societies, and the present paper catalogues some of the reptile species being used in Brazil and discusses implications for their conservation. A literature review indicated that 81 reptile species are culturally important in this country, with 47 (58%) species having multiple uses, 54 being used for medicinal purposes, 38 as food, 28 for ornamental or decorative purposes, 20 used in magic/religious practices, 18 as pets, and 40 are commonly killed when they come into contact with humans. Regarding their conservation status, 30 (37.5%) are included on State's Red List, Brazilian Red List or the IUCN Red List. There are many forms of interaction between reptiles and humans in Brazil-although most of them are quite negative in terms of wildlife conservation-which reinforces the importance of understanding such uses and interactions in the context of protecting reptiles in Brazil. A better understanding of the cultural, social, and traditional roles of these reptiles is fundamental to establishing management plans for their sustainable use.     

Urban activity and mercury contamination in estuarine and marine sediments (Southern Brazil)

The distribution of mercury in sediments of the Patos Lagoon estuary and nearby coastal marine deposits has been investigated for the period 1998-2008. Polluted urban soils and coastal reclamation fills are the principal sources of high mercury concentrations for shallow estuarine sediments. The shallow sediments that form near the urban area enter the navigation canal and are transported into the ocean. The mercury concentration in sediments of the navigation canal has considerably increased since 2004, due to intense reconstruction activity in the urban area. Periodic dredging of the canal strengthens the preconditions for coastal marine sediment contamination by mercury. However, this does not occur because the resuspended dredged sediments are significantly diluted by natural suspended particulate matter.     

Host-guest complexes of phenoxy alkyl acid herbicides and cyclodextrins. MCPA and β-cyclodextrin

The chlorophenoxy herbicide MCPA (4-chloro-2-methylphenoxyacetic acid), widely used for the control of broad-leaf weeds primarily in cereal and grass seed crops, still remains one of the most often used herbicides in Portugal. As the formation of inclusion complexes with cyclodextrins can improve its solubility properties, the interaction between the herbicide MCPA and β-cyclodextrin was investigated. The stability constants describing the extent of formation of the complexes have been determined by phase-solubility studies. Different analytical techniques [ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR)] were employed for a thorough investigation of the structural characteristics of the obtained complexes, which exhibited distinct features and properties from both “guest” and “host” molecules. FTIR and ¹H NMR data obtained for the MCPA/β-CD complexes gave information about the interaction between MCPA and the nonpolar cyclodextrin cavity. The dramatic change observed in band frequency and proton displacements of OCH₂ group and H6 aromatic proton confirmed the inclusion of MCPA in β-CD.

The formation of an inclusion complex between MCPA and β-CD increased the aqueous solubility of this herbicide which could be a particularly advantageous property for some specific applications, namely to improve commercial formulation and for environmental protection.     

Municipal solid waste shear strength parameters defined through laboratorial and in situ tests

This paper presents the parameters of municipal solid waste shear strength determined in the laboratory (triaxial tests) and by in situ tests: standard penetration tests (SPT) and cone penetration tests (CPT). The results analyzed here are part of a study carried out on the Santo Tirso landfill (north of Portugal) between 2001 and 2007. The influence of the strain levels, waste composition, and waste age on the shear strength parameters is presented, as well as an attempt to establish some correlations between the SPT and CPT tests and to estimate municipal solid waste (MSW) friction angles from the SPT tests. The results indicate that the aging of the waste, which is characterized by a decrease in fibrous and organic materials and an increase in inert materials and fine fraction, leads to an increase in frictional resistance and to a decrease in cohesion. The results of the SPT and CPT tests indicate higher penetration resistance in older and deeper waste. Estimating the frictional resistance from the SPT test seems to obey an empirical relationship expressed by a power function, which depends on the strain level.

Implications: Comparison of shear strength parameters of municipal solid waste (MSW) determined through laboratory (triaxial tests) and in situ tests (SPT and CPT) showed that the greater amount of fibrous and granular elements leads to an increase in “cohesion” and in friction angle values, respectively. Waste aging results in an increase in frictional resistance and in a decrease in “cohesive” resistance. This is consistent with the composition changes with aging: increase of the relative quantity of inert materials and fine fraction, and decrease in particle size, in organic matter content, and in fabrics and plastics.     

Ecosystem Impacts of Geoengineering: A Review for Developing a Science Plan

Geoengineering methods are intended to reduce climate change, which is already having demonstrable effects on ecosystem structure and functioning in some regions. Two types of geoengineering activities that have been proposed are: carbon dioxide (CO(2)) removal (CDR), which removes CO(2) from the atmosphere, and solar radiation management (SRM, or sunlight reflection methods), which reflects a small percentage of sunlight back into space to offset warming from greenhouse gases (GHGs). Current research suggests that SRM or CDR might diminish the impacts of climate change on ecosystems by reducing changes in temperature and precipitation. However, sudden cessation of SRM would exacerbate the climate effects on ecosystems, and some CDR might interfere with oceanic and terrestrial ecosystem processes. The many risks and uncertainties associated with these new kinds of purposeful perturbations to the Earth system are not well understood and require cautious and comprehensive research.     

Design,Engineering, and Construction of Photosynthetic Microbial Cell Factories for Renewable Solar Fuel Production

There is an urgent need to develop sustainable solutions to convert solar energy into energy carriers used in the society. In addition to solar cells generating electricity, there are several options to generate solar fuels. This paper outlines and discusses the design and engineering of photosynthetic microbial systems for the generation of renewable solar fuels, with a focus on cyanobacteria. Cyanobacteria are prokaryotic microorganisms with the same type of photosynthesis as higher plants. Native and engineered cyanobacteria have been used by us and others as model systems to examine, demonstrate, and develop photobiological H₂ production. More recently, the production of carbon-containing solar fuels like ethanol, butanol, and isoprene have been demonstrated. We are using a synthetic biology approach to develop efficient photosynthetic microbial cell factories for direct generation of biofuels from solar energy. Present progress and advances in the design, engineering, and construction of such cyanobacterial cells for the generation of a portfolio of solar fuels, e.g., hydrogen, alcohols, and isoprene, are presented and discussed. Possibilities and challenges when introducing and using synthetic biology are highlighted.     

Factors Influencing Allelopathy and Toxicity in Prymnesium parvum1

Granéli, Edna and Paulo S. Salomon, 2010. Factors Influencing Allelopathy and Toxicity in Prymnesium parvum. Journal of the American Water Resources Association (JAWRA) 46(1):108-120. Abstract: Some microalgae are able to kill or inhibit nutrient-competing microalgae, a process called allelopathy. Inhibiting or killing competitors enable these species to monopolize limiting resources, such as nitrogen and phosphorus. Prymnesium parvum is known to produce such allelopathic compounds, substances that seem identical to the ichthyotoxins identified from this species. Biotic and abiotic environmental factors influence not only growth rates but also toxin/allelopathic compounds production by P. parvum cells. Toxin production, as well as allelopathy, including grazer deterrence, increases dramatically in light, temperature, or nutrient stressed P. parvum cells. Correspondingly, toxicity and allelopathy may decrease, or cease completely, if cells are grown with high amounts of N and P in balanced proportions. However, even under nutrient (N and P) sufficient conditions, P. parvum is able to produce toxins/allelopathic compounds, with negative effects on other phytoplankton species or grazers, if cells densities of P. parvum are high relative to other species. This negative effect might shift the plankton community to more toxin resistant species. Filtrates from nutrient-deficient P. parvum cultures have almost the same strong negative effect on grazers and other phytoplankton species as when Prymnesium cells are grown together with the target organisms. Eutrophication, the increased input of N and P to aquatic ecosystems, besides increasing nutrient concentrations, is usually provoking unbalanced N:P condition for the optimal growth of phytoplankton, deviating from the Redfield ratio, i.e., the phytoplankton cellular nitrogen to phosphorus ratio, N:P = 16:1 (by atoms) or 7.2:1 (by weight). Eutrophication thus both enhances P. parvum growth and increases production of toxins and allelopathic compounds. Supplying N-deficient or P-deficient P. parvum cells with the deficient nutrient reduces toxicity to less than half within 24 h after additions. As P. parvum is mixotrophic, uptake of dissolved or particulate organic N (DON or PON) can also reduce toxicity and allelopathy in the same manner as addition of inorganic N to N-starved cells. In conclusion, P. parvum, by increasing its toxicity and allelopathic ability under poor environmental conditions, outcompetes the co-occurring phytoplankton species.     

Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.