Validation of a GC-MS/MS method for simultaneous determination of 86 persistent organic pollutants in marine sediments by pressurized liquid extraction followed by stir bar sorptive extraction

A multiresidue method for the analysis of 86 persistent pollutants in marine sediments at ultra-trace level has been developed and validated using pressurized liquid extraction (PLE) and stir-bar sorptive extraction (SBSE) coupled with thermal desorption and gas chromatography-triple quadrupole mass spectrometry (TD-GC-MS/MS QqQ). The compounds analyzed belong to various families such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenylethers, organophosphorus and organochlorine pesticides and other pesticides such as urons, and triazines. The analytes have very different polarities and log K_ow values, which is an important parameter in the optimization of a SBSE method. Due to PLE high efficiency and throughput rates, along with the proven ability for multiresidue analysis and excellent sensitivity of SBSE, we present an efficient method. The limits of quantification obtained ranged from 0.014 to 1.0 ng g⁻¹, with detection limits below pg g⁻¹ levels. In order to validate the proposed methodology, quality parameters such as recovery, linearity and reproducibility were studied. Recoveries ranged from 63% to 119%, reproducibility (in terms of Relative Standard Deviation for ten determinations) was lower than 35% in all cases, and determination coefficients higher than 0.990 for all analytes. The main factors that affect PLE, SBSE and GC-MS/MS procedures were optimized. The method was applied to the analysis of nine marine sediments obtained from the nine main submarine wastewater discharge points (emissaries) presents along the coast of Tenerife Island (Canary Islands, Spain).     

Anaerobic digestion of the liquid fraction of dairy manure in pilot plant for biogas production: residual methane yield of digestate

The performance of the only dairy manure biogas plant in Cantabria (Northern coast of Spain) was evaluated in terms of liquid-solid separation and anaerobic digestion of the liquid fraction. Screened liquid fraction was satisfactorily treated in a CSTR digester at HRTs from 20 to 10 days with organic loading rates ranging from 2.0 to 4.5 kg VS/(m(3)d). Stable biogas productions from 0.66 to 1.47 m(3)/(m(3)d) were achieved. Four anaerobic effluents collected from the digester at different HRTs were analyzed to measure their residual methane potentials, which ranged from 12.7 to 102.4 L/gVS. These methane potentials were highly influenced by the feed quality and HRT of the previous CSTR anaerobic digestion process. Biomethanization of the screened liquid fraction of dairy manure from intensive farming has the potential to provide up to 2% of total electrical power in the region of Cantabria.     

Thermophilic adaptation of a mesophilic anaerobic sludge for food waste treatment

As opposed to mesophilic, thermophilic anaerobic digestion of food waste can increase the biogas output of reactors. To facilitate the transition of anaerobic digesters, this paper investigated the impact of adapting mesophilic sludge to thermophilic conditions. A 5L bench scale reactor was seeded with mesophilic granular sludge obtained from an up-flow anaerobic sludge blanket digester. After 13 days of operation at 35 degrees C, the reactor temperature was instantaneously increased to 55 degrees C and operated at this temperature until day 21. The biomass was then fed food waste on days 21, 42 and 63, each time with an F/M (Food/Microorganism) ratio increasing from 0.12 to 4.43 gVS/gVSS. Sludge samples were collected on days 0, 21, 42 and 63 to conduct substrate activity tests, and reactor biogas production was monitored during the full experimental period. The sludge collected on day 21 demonstrated that the abrupt temperature change had no pasteurization effect, but rather lead to a biomass with a fermentative activity of 3.58 g Glucose/gVSS/d and a methanogenic activity of 0.47 and 0.26 g Substrate/gVSS/d, related respectively, to acetoclastic and hydrogenophilic microorganisms. At 55 degrees C, an ultimate gas production (Go) and a biodegradation potential (Bo) of 0.2-1.4 L(STP)/gVS(fed) and of 0.1-0.84 L(STP) CH(4)/gVS(fed) were obtained, respectively. For the treatment of food waste, a fully adapted inoculum was developed by eliminating the initial time-consuming acclimatization stage from mesophilic to thermophilic conditions. The feeding stage was initiated within 20 days, but to increase the population of thermophilic methanogenic microorganisms, a substrate supply program must be carefully observed.     

Land-Use Planning in the Chaco Plain (Burruyacú, Argentina). Part 1: Evaluating Land-Use Options to Support Crop Diversification in an Agricultural Frontier Area Using Physical Land Evaluation

The Burruyacú district (Tucumán province, Argentina) is a farming frontier in the western Chaco plain, at the foothills of the sub-Andean mountain ranges, where agricultural land-uses are in conflict with the conservation and management of the Chaco forest. Over the last decades, large-scale farming rapidly expanded due to population pressure, attractive market prices, easy accessibility, favourable annual rainfall, fertile soils, and flexible land tenure. Cropland extension, mainly for heavily mechanized soybean production, has resulted in important reduction of the Chaco forest and also caused physical soil degradation, especially soil compaction, and soil erosion. Land suitability was assessed using the Food and Agriculture Organization (FAO) framework for a set of crops ecologically adapted to the area, including soybean, maize, wheat, sugarcane, citrus, and safflower. Only 16% of the study area has high suitability for most of the selected crops. Major limitations for cropping are low annual rainfall and flooding in the east of the study area, and topography (slope) and flooding in the west. As climate varies over relatively short periods of time, with recurrent cycles of dry and rainy years, land suitability for the selected crops was also assessed under extreme but realistic climatic conditions. Under rainy-year conditions, almost all the study area is unsuitable or marginally suitable for most of the crops. Under dry-year conditions, the study area is unsuitable for all crops, except safflower, which is more drought-resistant. This article proposes alternatives to the mono-cropping of soybean with the aim to help farmers make adequate decisions on land-use and management under deteriorating environmental conditions and for addressing the issue of competitive land uses in the context of land-use planning.     

Application of the Fenton’s process in a bubble column reactor for hydroquinone degradation

The aim of this study was to assess the degradation and mineralization of hydroquinone (HQ) by the Fenton’s process in a bubble column reactor (BCR). The effect of the main operating variables, namely, air flow rate, effluent volume, hydrogen peroxide (H₂O₂) concentration, catalyst (Fe²⁺) dose, initial pH, and temperature, were assessed. For all air flow rates tested, no concentration gradients along the column were noticed, evidencing that a good mixing was reached in the BCR. For the best conditions tested ([H₂O₂] = 500 mg/L, [Fe²⁺] = 45 mg/L, T = 24 °C, Q _air = 2.5 mL/min, pH = 3.0, and V = 5 L), complete HQ degradation was reached, with ~ 39% of total organic carbon (TOC) removal, and an efficiency of the oxidant use—η _H2O2—of 0.39 (ratio between TOC removed per H₂O₂ consumed normalized by the theoretical stoichiometric value); moreover, a non-toxic effluent was generated. Under these conditions, the intermediates and final oxidation compounds identified and quantified were a few carboxylic acids, namely, maleic, pyruvic, and oxalic. As a strategy to improve the TOC removal, a gradual dosage of the optimal H₂O₂ concentration was implemented, being obtained ~ 55% of mineralization (with complete HQ degradation). Finally, the matrix effect was evaluated, for which a real wastewater was spiked with 100 mg/L of HQ; no reduction in terms of HQ degradation and mineralization was observed compared to the solution in distilled water.     

The invisibility of fisheries in the process of hydropower development across the Amazon

We analyze the invisibility of fisheries and inadequacy of fishers’ participation in the process of hydropower development in the Amazon, focusing on gaps between legally mandated and actual outcomes. Using Ostrom’s institutional design principles for assessing common-pool resource management, we selected five case studies from Brazilian Amazonian watersheds to conduct an exploratory comparative case-study analysis. We identify similar problems across basins, including deficiencies in the dam licensing process; critical data gaps; inadequate stakeholder participation; violation of human rights; neglect of fishers’ knowledge; lack of organization and representation by fishers’ groups; and lack of governmental structure and capacity to manage dam construction activities or support fishers after dam construction. Fishers have generally been marginalized or excluded from decision-making regarding planning, construction, mitigation, compensation, and monitoring of the social–ecological impacts of hydroelectric dams. Addressing these deficiencies will require concerted investments and efforts by dam developers, government agencies and civil society, and the promotion of inter-sectorial dialogue and cross-scale participatory planning and decision-making that includes fishers and their associations.     

Polarographic determination of the stability constant of the ternary complex formed between cocaine and cobalt thiocyanate

The interactions between cocaine -- Co(II) and thiocyanate (or dimethylglyoxime) have been studied by electrochemical means, assuming the existence of a ternary complex with the stoichiometry [(H₂O)₃Co(SCN)(C₁₇H₂₁NO₄)]⁺ and the absence of similar ternary species containing dimethylglyoxime. The formation constant of the complex has been evaluated by polarographic titrations because of the irreversibility of electrochemical processes. This relatively small value of 2.37 × 10⁵ is in agreement with the experimental conditions at which Scott's method is typically carried out to detect cocaine in solid samples by reaction with Co(II) thiocyanate.