Simultaneous and direct determination of glyphosate and AMPA in water samples from the hydroponic cultivation of eucalyptus seedlings using HPLC-ICP-MS/MS

Abstract

Glyphosate is the main herbicide currently used in the world due to wide applicability and efficiency in controlling weeds in many crops. However, its overuse may lead to undesirable impacts on the environment and to human health in the long run. This present study aimed to optimize and validate solid phase extraction (SPE) using an anionic resin for the simultaneous and direct determination of glyphosate and aminomethylphosphonic acid (AMPA) in water samples using high-performance liquid chromatography combined with inductively coupled plasma with triple quadrupole mass spectrometer (HPLC-ICP-MS/MS). The results showed that recovery percentage and relative standard deviation were 103.9?±?7.9 and 99.40?±?9.9% for glyphosate and AMPA, respectively. The validation certified that the method was precise, accurate, linear, and selective, with a limit of quantification of 1.09 and 0.29?μg L^?1 for glyphosate and AMPA, respectively. The optimized methodology reached the concentration factor of 250 times and was successfully applied to analyze water samples from hydroponic cultivation of the eucalyptus seedlings. The results showed that the exudation process occurs at glyphosate doses starting from 2?L ha^?1.     

Towards the selection of a produced water enrichment for biological gas hydrate inhibitors

Economic concerns associated with the recovery of non-conventional hydrocarbon reserves include unexpected ice as well as ice-like gas hydrate formation. Antifreeze proteins (AFPs) inhibit ice growth, and experiments with fish, plant, and insect AFPs have shown promise of effective gas hydrate inhibition in lab-scale experiments. If produced on an industrial scale, AFPs could provide a more environmentally friendly alternative to kinetic inhibitors, but a large-scale production of these AFPs is not currently feasible. We believe that these difficulties could be surmounted by the production of microbial AFPs, but to date, only a few such proteins have been identified and purified, and none of these are associated with hydrocarbon reserves. Here, we have used ice-affinity and freeze-thaw stress to select microbes derived from oil and gas formation water, or produced water, as a source of anaerobic microbial communities. Ice-affinity successfully incorporated anaerobic bacteria under aerobic conditions, and the mixed culture had ice-associating properties. Under these conditions, ice-affinity selection does not result in cultivatable isolates, but similar, cultivable microbes were obtained following freeze-thaw selection under anaerobic conditions. Since these mixed cultures inhibited the growth of ice crystals, they also have the potential to inhibit hydrate growth. Overall, freeze-thaw selection provides a promising first step towards the isolation of microbes capable of the inhibition of ice and gas hydrate growth, for possible application for energy exploration and recovery at high-latitudes and in-deep, cold waters.     

Degradation of caffeine by conductive diamond electrochemical oxidation

The use of Conductive-Diamond Electrochemical Oxidation (CDEO) and Sonoelectrochemical Oxidation (CDSEO) has been evaluated for the removal of caffeine of wastewater. Effects of initial concentration, current density and supporting electrolyte on the process efficiency are assessed. Results show that caffeine is very efficiently removed with CDEO and that depletion of caffeine has two stages depending on its concentration. At low concentrations, opposite to what it is expected in a mass-transfer controlled process, the efficiency increases with current density very significantly, suggesting a very important role of mediated oxidation processes on the removal of caffeine. In addition, the removal of caffeine is faster than TOC, indicating the formation of reaction intermediates. The number and relative abundance of them depend on the operating conditions and supporting electrolyte used. In chloride media, removal of caffeine is faster and more efficiently, although the occurrence of more intermediates takes place. CDSEO does not increase the efficiency of caffeine removal, but it affects to the formation of intermediates. A detailed characterization of intermediates by liquid chromatography time-of-flight mass spectrometry seems to indicate that the degradation of caffeine by CDEO follows an oxidation pathway similar to mechanism proposed by other advanced oxidation processes.     

What fraction of the organic carbon in sacoglossans is obtained from photosynthesis by kleptoplastids? An investigation using the natural abundance of stable carbon isotopes

any sacoglossans (opisthobranch gastropods) have the potential for carbon acquisition from photosynthesis by plastids sequestered from their macroalgal food as well as by ingestion, digestion and assimilation of the organic carbon derived from the alga. A new method for obtaining a minimum estimate of the fraction of sacoglossan carbon supplied from photosynthesis by kleptoplastids is suggested, based on the mass balance of stable carbon isotopes at the natural abundance level. The method involves comparison of ¹³C/¹²C ratios in sacoglossans with those of the algae on which they are found. Differences in ratios between alga and sacoglossan are used to give a minimum estimate of carbon acquisition by kleptoplasty, granted assumptions about the range of ¹³C/¹²C fractionation values which can occur for marine photolithotrophs. The new method is applied to several green (ulvophycean) alga–sacoglossan associations from Rottnest Island, Western Australia, and the values compared with those obtained previously by other means. The method suggests values of up to 0.6 of the total carbon input to the sacoglossans from photosynthesis by their kleptoplastids. To improve the estimates of the minimum role of kleptoplastidy in the carbon nutrition of sacoglossans, further information is needed: (1) on the fidelity of a given sacoglossan to a given algal individual (or species), (2) on the ¹³C/¹²C ratio of the part of the alga ingested by the sacoglossan, and (3) on the allocation of dietary organic carbon and of kleptoplastidic photosynthate to carbon lost in respiration, mucopolysaccharide production and gametes (and hence not sampled with the animal). Received: 24 November 1999 / Accepted: 20 October 2000     

Does seston size structure reflect fish-mediated effects on water quality in a degraded semiarid wetland?

This study evaluates whether the size structure of seston (the sum of living and nonliving particles in the water column) reflects the effects of fish on wetland water quality. Using enclosures, we measured water quality and zooplankton community structure in the presence and absence of two fish species with distinct foraging strategies [benthivorous carp (Cyprinus carpio) and planktivorous mosquitofish (Gambusia holbrooki)]. Seston collected from the enclosures was counted and sized automatically with a Coulter counter, and the size structure in the range of 1–60 μm was modelled using the underlying Pareto distribution of particles. Only Cyprinus contributed to a loss of water quality (increased nutrient levels, algal and non-algal turbidity, hypoxia), while both fish species changed zooplankton community composition compared to fishless controls. However, these changes were not reflected in parameters [goodness of fit (r ²) and parameter c (slopes)] of Pareto models. Multivariate statistics suggest that seston size structure responded more to environmental gradients related to water depth but the relationships were also weak. Our overall result contrasts with the regulation of size spectra constructed from living organisms. Although seston integrates many structural and functional features of the water column, the lack of strong relationships between Pareto model parameters and water quality suggests that a size-based approach to characterise seston structure has a limited potential for assessing biota-mediated effects in wetlands in a straightforward manner.     

Atmospheric Monitoring at Abandoned Mercury Mine Sites in Asturias (NW Spain)

Mercury concentrations are usually significant in historic Hg mining districts all over the world, so the atmospheric environment is potentially affected. In Asturias, northern Spain, past mining operations have left a legacy of ruins and Hg-rich wastes, soils and sediments in abandoned sites. Total Hg concentrations in the ambient air of these abandoned mine sites have been investigated to evaluate the impact of the Hg emissions. This paper presents the synthesis of current knowledge about atmospheric Hg contents in the area of the abandoned Hg mining and smelting works at ‘La Peña–El Terronal’ and La Soterraña, located in Mieres and Pola de Lena districts, respectively, both within the Caudal River basin. It was found that average atmospheric Hg concentrations are higher than the background level in the area (0.1 μg Nm^?3), reaching up to 203.7 μg Nm^?3 at 0.2 m above the ground level, close to the old smelting chimney at El Terronal mine site. Data suggest that past Hg mining activities have big influences on the increased Hg concentrations around abandoned sites and that atmospheric transfer is a major pathway for Hg cycling in these environments.     

Monitoring water quality in Sydney Harbour using blue mussels during remediation of the Sydney Tar Ponds,Nova Scotia,Canada

Using mussels as monitoring tools we measured water quality in Sydney Harbour during a large scale, multi-year remediation project of the Sydney Tar Ponds (STPs); one of Canada's most contaminated sites. Chemical contaminants were measured in blue mussels (Mytilus edulis) in Sydney Harbour, which were used as monitoring tools to assess the spatio-temporal distribution of polycyclic aromatic hydrocarbons (PAHs); polychlorinated biphenyls (PCBs); metals (As, Cd, Cu, Hg, Pb, Zn) and lipid content during baseline and 3 years of remediation. The overall spatio-temporal distribution of chemicals in mussels was also compared to contaminants in other marine indicators (e.g., sediment, water and crab tissue). Measured metal concentrations in mussels showed some minor temporal variability (4 years), but these did not appear to be directly related to remediation activities, with the highest concentrations of As, Hg and Zn measured at reference stations. Most measured contaminants showed stable or potentially decreasing concentrations during the study, except Pb and Zn. Individual PAH compounds were mostly undetected during baseline and remediation, except for fluoranthene and pyrene. Concentrations of fluoranthene in mussels and deep water samples were moderately related. Generally, PCBs were undetected (<0.05 μg g^?1), except during year 2 remediation at some near-field stations. Contaminants measured during this study were at much lower concentrations than previously reported in other studies of mussels in Sydney Harbour and eastern Canada. This is likely due to the ongoing natural recovery of Sydney Harbour and to a lesser extent because of the environmental mitigation protection measures implemented during remediation activities at the STPs. The lack of detection of most individual PAHs and PCBs, plus relatively low bio-accumulation of metals observed during baseline and remediation attest to the effectiveness of using mussels as monitoring tools for environmental quality.     

Monitoring effects of remediation on natural sediment recovery in Sydney Harbour, Nova Scotia

Chemical contaminants were assessed in Sydney Harbour, Nova Scotia during pre-remediation (baseline) and 3 years of remediation of a former coking and steel facility after nearly a century of operation and historical pollution into the Sydney Tar Ponds (STP). Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, metals, and inorganic parameters measured in sediments and total suspended solids in seawater indicate that the overall spatial distribution pattern of historical contaminants remains unchanged, although at much lower concentrations than previously reported due to natural sediment recovery, despite remediation activities. Measured sediment deposition rates in bottom-moored traps during baseline were low (0.4–0.8 cm?year^?1), but during dredging operations required for construction of new port facilities in the inner Sydney Harbour, sedimentation rates were equivalent to 26–128 cm year^?1. Measurements of sediment chemical contaminants confirmed that natural recovery rates of Sydney Harbour sediments were in broad agreement with predicted concentrations, or in some cases, lower than originally predicted despite remediation activities at the STP site. Overall, most measured contaminants in sediments showed little temporal variability (4 years), except for the detection of significant increases in total PAH concentrations during the onset of remediation monitoring compared to baseline. This slight increase represents only a short-term interruption in the overall natural recovery of sediments in Sydney Harbour, which were enhanced due to the positive impacts of large-scale dredging of less contaminated outer harbor sediments which were discharged into a confined disposal area located in the inner harbor.     

Effects of residual antibiotics in groundwater on Salmonella typhimurium: changes in antibiotic resistance, in vivo and in vitro pathogenicity

An outbreak-causing strain of Salmonella enterica serovar Typhimurium was exposed to groundwater with residual antibiotics for up to four weeks. Representative concentrations (0.05, 1, and 100 μg L(-1)) of amoxicillin, tetracycline, and a mixture of several other antibiotics (1 μg L(-1) each) were spiked into artificially prepared groundwater (AGW). Antibiotic susceptibility analysis and the virulence response of stressed Salmonella were determined on a weekly basis by using human epithelial cells (HEp2) and soil nematodes (C. elegans). Results have shown that Salmonella typhimurium remains viable for long periods of exposure to antibiotic-supplemented groundwater; however, they failed to cultivate as an indication of a viable but nonculturable state. Prolonged antibiotics exposure did not induce any changes in the antibiotic susceptibility profile of the S. typhimurium strain used in this study. S. typhimurium exposed to 0.05 and 1 μg L(-1) amoxicillin, and 1 μg L(-1) tetracycline showed hyper-virulent profiles in both in vitro and in vivo virulence assays with the HEp2 cells and C. elegans respectively, most evident following 2nd and 3rd weeks of exposure.     

Source apportionment in oil spill remediation

A pipe rupture during unloading led to a spillage of 350-700 tonnes of Ca?o Limon, a light sweet crude oil, into San Vicente Bay in 2007. Initial clean-up methods removed the majority of the oil from the sandy beaches although some oil remained on the rocky shores. It was necessary for the responsible party to clean the spilled oil even though at this location there were already crude oil hydrocarbons from previous industrial activity. A biosolvent based on vegetable oil derivatives was used to solubilise the remaining oil and a statistical approach to source apportionment was used to determine the efficacy of the cleaning. Sediment and contaminated rock samples were taken prior to cleaning and again at the same locations two days after application of the biosolvent. The oil was extracted using a modified USEPA Method 3550B. The alkanes were quantified together with oil biomarkers on a GC-MS. The contribution that Ca?o Limon made to the total oil hydrocarbons was calculated from a Partial Least Squares (PLS) analysis using Ca?o Limon crude oil as the source. By the time the biosolvent was applied, there had already been some attenuation of the oil with all alkanes 相似文献