Short-term impact of olive mill wastewater (OMWW) applications on the physico-chemical and microbiological soil properties of an olive grove in Argentina

The purpose of this work was to investigate the effects of spreading olive oil mill wastewater (OMWW) on soil biochemical parameters and olive production in an organically managed olive orchard. The experiment was carried out with three different doses of OMWW (80, 160 and 500 m³ ha^?1) and a control (untreated soil). Three samplings were done at 10, 30 and 90 days after the administration of the byproduct. OMWW application differentially modified the biochemical properties of the soil analyzed. Organic matter, organic carbon, total nitrogen and extractable phosphorus soil contents increased proportionally with each increasing dose. The values of these parameters decreased gradually with time. Total microbial activity was altered and the OMWW 500 m³ ha^?1 treatment proved to be the most active when compared with the other applied doses. OMWW agricultural application also modified the structure of soil microbial communities, particularly affecting Gram positive and negative bacteria, while fungal biomass did not show consistent changes. Although there was a salinity increase in the treated soil, especially at the highest dose, the productive parameters analyzed (fruit and oil tree^?1) were not affected. In light of the obtained results, we consider that low dose of OMWW could be considered an alternative farming practice for semiarid regions.     

Estimate of the uncertainty in measurement for the determination of mercury in seafood by TDA AAS

An approach for the estimate of the uncertainty in measurement considering the individual sources related to the different steps of the method under evaluation as well as the uncertainties estimated from the validation data for the determination of mercury in seafood by using thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) is proposed. The considered method has been fully optimized and validated in an official laboratory of the Ministry of Agriculture, Livestock and Food Supply of Brazil, in order to comply with national and international food regulations and quality assurance. The referred method has been accredited under the ISO/IEC 17025 norm since 2010. The approach of the present work in order to reach the aim of estimating of the uncertainty in measurement was based on six sources of uncertainty for mercury determination in seafood by TDA AAS, following the validation process, which were: Linear least square regression, Repeatability, Intermediate precision, Correction factor of the analytical curve, Sample mass, and Standard reference solution. Those that most influenced the uncertainty in measurement were sample weight, repeatability, intermediate precision and calibration curve. The obtained result for the estimate of uncertainty in measurement in the present work reached a value of 13.39%, which complies with the European Regulation EC 836/2011. This figure represents a very realistic estimate of the routine conditions, since it fairly encompasses the dispersion obtained from the value attributed to the sample and the value measured by the laboratory analysts. From this outcome, it is possible to infer that the validation data (based on calibration curve, recovery and precision), together with the variation on sample mass, can offer a proper estimate of uncertainty in measurement.     

Land-use and land-cover effects on regional biodiversity distribution in a subtropical dry forest: a hierarchical integrative multi-taxa study

Latin American subtropical dry ecosystems have experienced significant human impact for more than a century, mainly in the form of extensive livestock grazing, forest products extraction, and agriculture expansion. We assessed the regional-scale effect of land use and land cover (LULC) on patterns of richness distribution of trees, birds, amphibians, and mammals in the Northern Argentine Dry Chaco (NADC) over c. 19 million hectares. Using species distribution models in a hierarchical framework, we modeled the distributions of 138 species. First, we trained the models for the entire Argentinean Chaco with climatic and topographic variables. Second, we modeled the same species for the NADC including the biophysical variables identified as relevant in the first step plus four LULC-related variables: woody biomass, distance to crops, density of livestock-based rural settlements (puestos), and vegetation cover. Third, we constructed species richness maps by adding the models of individual species and considering two situations, with and without LULC variables. Four, richness maps were used for assessing differences when LULC variables are added and for determining the main drivers of current patterns of species richness. We found a marked decrease in species richness of the four groups as a consequence of inclusion of LULC variables in distribution models. The main factors associated with current richness distribution patterns (both negatively) were woody biomass and density of livestock puestos. Species richness in present-day Semiarid Chaco landscapes is strongly affected by LULC patterns, even in areas not transformed to agriculture. Regional-scale biodiversity planning should consider open habitats such as grasslands and savannas in addition to woodlands.     

Lead isotope ratios in lichen samples evaluated by ICP-ToF-MS to assess possible atmospheric pollution sources in Havana,Cuba

Epiphytic lichens, collected from 119 sampling sites grown over “Roistonea Royal Palm” trees, were used to assess the spatial distribution pattern of lead (Pb) and identify possible pollution sources in Havana (Cuba). Lead concentrations in lichens and topsoils were determined by flame atomic absorption spectrophotometry and inductively coupled plasma (ICP) atomic emission spectrometry, respectively, while Pb in crude oils and gasoline samples were measured by ICP-time of flight mass spectrometry (ICP-ToF-MS). Lead isotopic ratios measurements for lichens, soils, and crude oils were obtained by ICP-ToF-MS. We found that enrichment factors (EF) reflected a moderate contamination for 71% of the samples (EF > 10). The ²⁰⁶Pb/²⁰⁷Pb ratio values for lichens ranged from 1.17 to 1.20 and were a mixture of natural radiogenic and industrial activities (e.g., crude oils and fire plants). The low concentration of Pb found in gasoline (<7.0 μg L^?1) confirms the official statement that leaded gasoline is no longer used in Cuba.     

Detection of hormones in surface and drinking water in Brazil by LC-ESI-MS/MS and ecotoxicological assessment with <Emphasis Type="Italic">Daphnia magna</Emphasis>

The growing use of pharmaceutical drug is mainly due to several diseases in human and in animal husbandry. As these drugs are discharged into waterways via wastewater, they cause a major impact on the environment. Many of these drugs are hormones; in which even at low concentrations can alter metabolic and physiological functions in many organisms. Hormones were found in surface water, groundwater, soil, and sediment at concentrations from nanograms to milligrams per liter of volume—quantities known to cause changes in the endocrine system of aquatic organisms. This study aimed to develop a methodology for hormone detection (estriol, estrone, 17β-estradiol, 17α-ethinylestradiol, progesterone, and testosterone) on surface and treated water samples. Sample toxicity was assessed by ecotoxicology tests using Daphnia magna. A liquid chromatograph coupled to a mass spectrometer with an electrospray ionization source (LC-ESI-MS/MS) was used for the analysis. The results showed that samples were contaminated by the hormones estriol, estrone, progesterone, 17β-estradiol, and 17α-ethinylestradiol during the sampling period, and the highest concentrations measured were 90, 28, 26, 137, and 194 ng·L^?1, respectively. This indicates the inflow of sewage containing these hormones at some points in the Piracicaba River in the State of Sao Paulo—Brazil. Results indicated little toxicity of the hormone estriol in D. magna, indicating that chronic studies with this microcrustacean are necessary.     

Trace level determination of selected organophosphorus pesticides and their degradation products in environmental air samples by liquid chromatography-positive ion electrospray tandem mass spectrometry

This paper describes a new analytical method for determination of organophosphorus pesticides (OPs) along with their degradation products involving liquid chromatography (LC) positive ion electrospray (ESI+) tandem mass spectrometry (MS-MS) with selective reaction monitoring (SRM). Chromatography was performed on a Gemini C6-Phenyl (150 mmx2.0 mm, 3 microm) with a gradient elution using water-methanol with 0.1% formic acid, 2 mM ammonium acetate mobile phase at a flow rate of 0.2 mL min(-1). The LC separation and MS/MS operating conditions were optimized with a total analysis time less than 40 minutes. Method detection limits of 0.1-5 microg L(-1) for selected organophosphorus pesticides (OP), OP oxon degradation products, and other degradation products: 3,5,6-trichloro-2-pyridinol (TCP); 2-isopropyl-6-methyl-4-pyrimidol (IMP); and diethyl phosphate (DEP). Some OPs such as fenchlorphos are less sensitive (MDL 30 microg L(-1)). Calibration curves were linear with coefficients of correlation better than 0.995. A three-point identification approach was adopted with area from first selective reaction monitoring (SRM) transition used for quantitative analysis, while a second SRM transition along with the ratio of areas obtained from the first to second transition are used for confirmation with sample tolerance established by the relative standard deviation of the ratio obtained from standards. This new method permitted the first known detection of OP oxon degradation products including chlorpyrifos oxon at Bratt's Lake, SK and diazinon oxon and malathion oxon at Abbotsford, BC in atmospheric samples. Atmospheric detection limits typically ranged from 0.2-10 pg m(-3).     

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.     

Pesticides in the surface waters of the Camanducaia River watershed,Brazil

Abstract

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4?mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57?μg L^?1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5?m y^?1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.