Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC–MS–MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [¹³C₆]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO’s behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 μg l⁻¹) to final effluent (4 μg l⁻¹), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 μg l⁻¹. In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 μg l⁻¹. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 μg l⁻¹) and NP0-1EC (4.8 μg l⁻¹) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest.     

Using FTIR to corroborate the identity of functional groups involved in the binding of Cd and Cr to saltbush (Atriplex canescens) biomass

Fourier transform infrared (FTIR) studies were performed to confirm the chemical modification of saltbush (Atriplex canescens) biomass and to provide information about the identity and binding characteristics of the chemical groups responsible for the binding of Cd(II), Cr(III), and Cr(VI). In addition, studies were performed to determine the optimum time for the binding of the three ions by saltbush biomass, and to study the efficiency of HCl and sodium citrate as stripping agents. The metal quantification was performed using inductively coupled plasma optical emission spectroscopy (ICP-OES). The results showed that 10 min or less is enough to achieve the maximum metal binding, and that aqueous solutions of 0.1 mM HCl or sodium citrate were enough to strip more than 80% of the bound Cd. It was determined that more than 70% of the bound Cr(III) was stripped using 0.1 mM HCl. Chemical modification of carboxyl and ester groups on the biomass was performed. The FTIR results confirmed that the esterification of carboxyl groups and hydrolysis of ester groups in the native biomass had occurred. The direct effect of these modifications on the binding properties of the biomass provided strong evidence that the carboxyl functionality is the main group responsible for binding Cd and Cr(III). However, the IR data showed that for Cr(VI), a different type of functional group is involved.     

Mineralization of paracetamol in aqueous medium by anodic oxidation with a boron-doped diamond electrode

The degradation of 100ml of solutions with paracetamol (N-(4-hydroxyphenyl)acetamide) up to 1 g l(-1) in the pH range 2.0-12.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a graphite cathode, both of 3-cm2 area, by applying a current of 100, 300 and 450 mA between 25 and 45 degrees C. Complete mineralization is always achieved due to the great concentration of hydroxyl radical (*OH) generated at the BDD surface, with release of NH4+ and NO3- ions. The mineralization rate is pH-independent, increases with increasing applied current and temperature, but decreases when drug concentration raises from 315 mg l(-1). Reversed-phase chromatography revealed a similar complex paracetamol decay in acid and alkaline media. Ion-exclusion chromatography allowed the detection of oxalic and oxamic acids as ultimate carboxylic acids. When the same solutions have been comparatively treated with a Pt anode, a quite poor mineralization is found because of the production of much lower *OH concentration. Under these conditions, the degradation rate is enhanced in alkaline medium and polymerization of intermediates is favored in concentrated solutions. Paracetamol can be completely destroyed with Pt and its kinetics follows a pseudo-first-order reaction with a constant rate independent of pH.     

Prediction of potential areas of species distributions based on presence-only data

We introduce a methodology to infer zones of high potential for the habitat of a species, useful for management of biodiversity, conservation, biogeography, ecology, or sustainable use. Inference is based on a set of sites where the presence of the species has been reported. Each site is associated with covariate values, measured on discrete scales. We compute the predictive probability that the species is present at each node of a regular grid. Possible spatial bias for sites of presence is accounted for. Since the resulting posterior distribution does not have a closed form, a Markov chain Monte Carlo (MCMC) algorithm is implemented. However, we also describe an approximation to the posterior distribution, which avoids MCMC. Relevant features of the approach are that specific notions of data acquisition such as sampling intensity and detectability are accounted for, and that available a priori information regarding areas of distribution of the species is incorporated in a clear-cut way. These concepts, arising in the presence-only context, are not addressed in alternative methods. We also consider an uncertainty map, which measures the variability for the predictive probability at each node on the grid. A simulation study is carried out to test and compare our approach with other standard methods. Two case studies are also presented.     

Carbon storage in Amazonia during the last glacial maximum: secondary data and uncertainties

The Amazonian forest is, due to its great size, carbon storage capacity and present-day variability in carbon uptake and release, an important component of the global carbon cycle. Paleo-environmental reconstruction is difficult for Amazonia due to the scarcity of primary palynological data and the mis-interpretation of some secondary data. Studies of lacustrine sediment records have shown that Amazonia has known periods in which the climate was drier than it is today. However, not all geomorphological features such as dunes, and slope erosion, which are thought to indicate rainforest regression, date from the time of the Late Glacial Maximum (LGM) and these features do not necessarily correspond to episodes of forest regression. There is also uncertainty concerning LGM carbon storage due to rainforest soils and biomass estimates. Soil carbon content may decrease moderately during the LGM, whereas rainforest biomass may change considerably in response to changes in the global environment. Biomass per unit area in Amazonia has probably been reduced by the cumulative effects of low CO2 concentration, a drier climate and lower temperatures. As few paleo-vegetation data are available, there is considerable uncertainty concerning the amount of carbon stored in Amazonia during the LGM, which may have corresponded to 44-94% of the carbon currently stored in biomass and soils.     

Efficient and equitable design of marine protected areas in Fiji through inclusion of stakeholder‐specific objectives in conservation planning

The efficacy of protected areas varies, partly because socioeconomic factors are not sufficiently considered in planning and management. Although integrating socioeconomic factors into systematic conservation planning is increasingly advocated, research is needed to progress from recognition of these factors to incorporating them effectively in spatial prioritization of protected areas. We evaluated 2 key aspects of incorporating socioeconomic factors into spatial prioritization: treatment of socioeconomic factors as costs or objectives and treatment of stakeholders as a single group or multiple groups. Using as a case study the design of a system of no‐take marine protected areas (MPAs) in Kubulau, Fiji, we assessed how these aspects affected the configuration of no‐take MPAs in terms of trade‐offs between biodiversity objectives, fisheries objectives, and equity in catch losses among fisher stakeholder groups. The achievement of fisheries objectives and equity tended to trade‐off concavely with increasing biodiversity objectives, indicating that it is possible to achieve low to mid‐range biodiversity objectives with relatively small losses to fisheries and equity. Importantly, the extent of trade‐offs depended on the method used to incorporate socioeconomic data and was least severe when objectives were set for each fisher stakeholder group explicitly. We found that using different methods to incorporate socioeconomic factors that require similar data and expertise can result in plans with very different impacts on local stakeholders.     

The value of open ocean ecosystems: A case study for the Spanish exclusive economic zone

Valuing goods and services from open oceans provides arguments for the ocean's protection and plays an increasingly important role in debates on the use and management of natural resources. This paper identifies and estimates the monetary value of some of the most important goods and services provided by open oceans. The list of goods and services considered includes food production, raw materials, water supply, CO₂ regulation, bioremediation of waste, biomass and biodiversity conservation. Therefore, not only values associated with productive uses are quantified but also values assigned to other biological ecosystem services. This paper constitutes a first attempt in the open ocean literature at evaluating services such as water supply, biomass and biodiversity conservation. To obtain their monetary value, different techniques, some not applied before in this area, have been used depending on the ecosystem service to be evaluated. As a general criterion we use the concept of net value added (revenues obtained from the services less incurred costs). Our methodology is illustrated by estimating the monetary values of goods and services provided by the open ocean ecosystem of Spain as defined by its exclusive economic zone. The total economic value obtained measures the contribution of oceans to overall welfare and it may be an important instrument in managing open ocean ecosystems and developing environmental policies in the future.     

Ecosystem development in roadside grasslands: biotic control, plant-soil interactions, and dispersal limitations

Roadside grasslands undergoing secondary succession are abundant, and represent ecologically meaningful examples of novel, human-created ecosystems. Interactions between plant and soil communities (hereafter plant-soil interactions) are of major importance in understanding the role of biotic control in ecosystem functioning, but little is known about these links in the context of ecosystem restoration and succession. The assessment of the key biotic communities and interactions driving ecosystem development will help practitioners to better allocate the limited resources devoted to roadside grassland restoration. We surveyed roadside grasslands from three successional stages (0-2, 7-9, and >20 years) in two Mediterranean regions of Spain. Structural equation modeling was used to evaluate how interactions between plants, biological soil crusts (BSCs), and soil microbial functional diversity (soil microorganisms) affect indicators of ecosystem development and restoration: plant similarity to the reference ecosystem, erosion control, and soil C storage and N accumulation. Changes in plant community composition along the successional gradient exerted the strongest influence on these indicators. High BSC cover was associated with high soil stability, and high soil microbial functional diversity from late-successional stages was associated with high soil fertility. Contrary to our expectations, the indirect effects of plants, mediated by either BSCs or soil microorganisms, were very weak in both regions, suggesting a minor role for plant-soil interactions upon ecosystem development indicators over long periods. Our results suggest that natural vegetation dynamics effectively improved ecosystem development within a time frame of 20 years in the grasslands evaluated. They also indicate that this time could be shortened if management actions focus on: (1) maintaining well-conserved natural areas close to roadsides to enhance plant compositional changes towards late-successional stages, (2) increasing BSC cover in areas under strong erosion risk, to avoid soil loss, and (3) enhancing soil microbial functional diversity in resource-limited areas, to enhance soil C and N accumulation.