An integrated approach for assessing the migration behavior of chlorpyrifos and carbaryl in the unsaturated soil zone

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (K_D) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg^?1) and carbaryl (3.1 and 4.2 L kg^?1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.     

Grab and passive sampling applied to pesticide analysis in the São Lourenço river headwater in Campo Verde – MT,Brazil

In this study, the quality of surface water in the headwaters of São Lourenço River in Mato Grosso, Brazil, was evaluated in relation to contamination by pesticides. For this purpose, samples were collected between December 2015 and June 2016 by grab sampling and by passive sampling using an integrative polar organic compound sampler installed in the field during four 14-day cycles between March and June 2016. The analyses were performed by gas chromatography (CG/MS) and by liquid chromatography (UPLC-MS/MS). The results showed the detection of two pesticides (atrazine and pyraclostrobin) of the five analyzed by passive sampling and eight active principles among the 20 analyzed (malathion, diuron, carbofuran, carbendazim, trifluralin, imidacloprid, metolachlor, and acetamiprid) by grab sampling. The detection of 10 pesticides, even almost a decade after the beginning of a recovery process of the ciliary forest, confirms the headwaters' vulnerability to these contaminants and passive sampling proved to be an important tool in capturing small concentrations of pesticides constituting an interesting complement to grab sampling.     

Long-term dispersion and availability of metals from submarine mine tailing disposal in a fjord in Arctic Norway

Mining of Cu took place in Kvalsund in the Arctic part of Norway in the 1970s, and mine tailings were discharged to the inner part of the fjord, Repparfjorden. Metal speciation analysis was used to assess the historical dispersion of metals as well as their potential bioavailability from the area of the mine tailing disposal. It was revealed that the dispersion of Ba, Cr, Ni, Pb and Zn from the mine tailings has been limited. Dispersion of Cu to the outer fjord has, however, occurred; the amounts released and dispersed from the mine tailing disposal area quantified to be 2.5–10 t, less than 5% of Cu in the original mine tailings. An estimated 80–390 t of Cu still remains in the disposal area from the surface to a depth of 16 cm. Metal partitioning showed that 56–95% of the Cu is bound in the potential bioavailable fractions (exchangeable, reducible and oxidisable) of the sediments, totalling approximately 70–340 t, with potential for continuous release to the pore water and re-precipitation in over- and underlying sediments. Surface sediments in the deposit area were affected by elevated Cu concentrations just above the probable effect level according to the Norwegian sediment quality criteria, with 50–80% Cu bound in the exchangeable, reducible and oxidisable fractions, potentially available for release to the water column and/or for uptake in benthic organisms.     

Pond bank access as an approach for managing toxic cyanobacteria in beef cattle pasture drinking water ponds

Forty-one livestock drinking water ponds in Alabama beef cattle pastures during were surveyed during the late summer to generally understand water quality patterns in these important water resources. Since livestock drinking water ponds are prone to excess nutrients that typically lead to eutrophication, which can promote blooms of toxigenic phytoplankton such as cyanobacteria, we also assessed the threat of exposure to the hepatotoxin, microcystin. Eighty percent of the ponds studied contained measurable microcystin, while three of these ponds had concentrations above human drinking water thresholds set by the US Environmental Protection Agency (i.e., 0.3 μg/L). Water quality patterns in the livestock drinking water ponds contrasted sharply with patterns typically observed for temperate freshwater lakes and reservoirs. Namely, we found several non-linear relationships between phytoplankton abundance (measured as chlorophyll) and nutrients or total suspended solids. Livestock had direct access to all the study ponds. Consequently, the proportion of inorganic suspended solids (e.g., sediment) increased with higher concentrations of total suspended solids, which underlies these patterns. Unimodal relationships were also observed between microcystin and phytoplankton abundance or nutrients. Euglenoids were abundant in the four ponds with chlorophyll concentrations >?250 μg/L (and dominated three of these ponds), which could explain why ponds with high chlorophyll concentrations would have low microcystin concentrations. Based on observations made during sampling events and available water quality data, livestock-mediated bioturbation is causing elevated total suspended solids that lead to reduced phytoplankton abundance and microcystin despite high concentrations of nutrients, such as phosphorus and nitrogen. Thus, livestock could be used to manage algal blooms, including toxic secondary metabolites, in their drinking water ponds by allowing them to walk in the ponds to increase turbidity.     

FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al₂O₃) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L^?1 for H₂SO₄ concentration, system flow rate as 0.40 mL min^?1, sample injection volume of 192.50 μL, 2 min for preconcentration time, and 0.10 mol L^?1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 μM, linear correlation coefficient R?=?0.9997 and LOD?=?0.024 μM. The preconcentration factor of about four times was obtained through the passage of 800 μL of a standard solution containing 0.961 μM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 μL of NH₄OH 0.1 mol L^?1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 μL of HCl 0.02 mol L^?1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.     

Urban tracer dispersion experiments during the second DAPPLE field campaign in London 2004

As part of the DAPPLE programme two large scale urban tracer experiments using multiple simultaneous releases of cyclic perfluoroalkanes from fixed location point sources was performed. The receptor concentrations along with relevant meteorological parameters measured are compared with a three screening dispersion models in order to best predict the decay of pollution sources with respect to distance. It is shown here that the simple dispersion models tested here can provide a reasonable upper bound estimate of the maximum concentrations measured with an empirical model derived from field observations and wind tunnel studies providing the best estimate. An indoor receptor was also used to assess indoor concentrations and their pertinence to commonly used evacuation procedures.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Climate Policy to Defeat the Green Paradox

Carbon dioxide emissions have accelerated since the signing of the Kyoto Protocol. This discouraging development may partly be blamed on accelerating world growth and on lags in policy instruments. However, it also raises serious question concerning whether policies to reduce CO₂ emissions are as effective as generally assumed. In recent years, a considerable number of studies have identified various feedback mechanisms of climate policies that often erode, and occasionally reinforce, their effectiveness. These studies generally focus on a few feedback mechanisms at a time, without capturing the entire effect. Partial accounting of policy feedbacks is common in many climate scenarios. The IPCC, for example, only accounts for direct leakage and rebound effects. This article attempts to map the aggregate effects of different types of climate policy feedback mechanisms in a cohesive framework. Controlling feedback effects is essential if the policy measures are to make any difference on a global level. A general conclusion is that aggregate policy feedback mechanisms tend to make current climate policies much less effective than is generally assumed. In fact, various policy measures involve a definite risk of ‘backfiring’ and actually increasing CO₂ emissions. This risk is particularly pronounced once effects of climate policies on the pace of innovation in climate technology are considered. To stand any chance of controlling carbon emissions, it is imperative that feedback mechanisms are integrated into emission scenarios, targets for emission reduction and implementation of climate policy. In many cases, this will reduce the scope for subsidies to renewable energy sources, but increase the scope for other measures such as schemes to return carbon dioxide to the ground and to mitigate emissions of greenhouse gases from wetlands and oceans. A framework that incorporates policy feedback effects necessitates rethinking the design of the national and regional emission targets. This leads us to a new way of formulating emission targets that include feedback effects, the global impact target. Once the full climate policy feedback mechanisms are accounted for, there are probably only three main routes in climate policy that stand a chance of mitigating global warming: (a) returning carbon to the ground, (b) technological leaps in zero-emission energy technology that make it profitable to leave much carbon in the ground even in Annex II countries and (c) international agreements that make it more profitable to leave carbon in the ground or in forests.     

Will photosynthetic capacity of aspen trees acclimate after long-term exposure to elevated CO2 and O3?

Photosynthetic acclimation under elevated carbon dioxide (CO₂) and/or ozone (O₃) has been the topic of discussion in many papers recently. We examined whether or not aspen plants grown under elevated CO₂ and/or O₃ will acclimate after 11 years of exposure at the Aspen Face site in Rhinelander, WI, USA. We studied diurnal patterns of instantaneous photosynthetic measurements as well as A/C_i measurements monthly during the 2004-2008 growing seasons. Our results suggest that the responses of two aspen clones differing in O₃ sensitivity showed no evidence of photosynthetic and stomatal acclimation under either elevated CO₂, O₃ or CO₂ + O₃. Both clones 42E and 271 did not show photosynthetic nor stomatal acclimation under elevated CO₂ and O₃ after a decade of exposure. We found that the degree of increase or decrease in the photosynthesis and stomatal conductance varied significantly from day to day and from one season to another.     

Identification of microcystins from three collection strains of Microcystis aeruginosa

Microcystins (MCs) are toxic cyclic heptapeptides produced by various cyanobacteria genera, especially Microcystis. We identified 10 out of 12 MCs produced by three Microcystis aeruginosa strains from cyanobacteria collections, UTEX 2666, UTEX 2670 and UAM 1303, by using two analytical methods: Matrix-assisted Laser Desorption Ionization Time of Flight Mass Spectrometry (MALDI-TOF/MS) and HPLC Photodiode Array Detector coupled to a hybrid Quadrupole Time of Flight Mass Spectrometry (HPLC-PDA-QTOF/MS). MALDI-TOF/MS failed to detect non-polar MCs, such as MC-LY and MC-LW. HPLC-QTOF/MS permitted the accurate identification of most MCs present in methanolic extracts. Besides, three new MCs, namely: [D-Glu(OCH₃)⁶, D-Asp³] MC-LAba, MC-YL and MC-YM were detected by HPLC-QTOF/MS.