An approach for restoration of the water quality with emphasis on the removal of organochlorine pesticides and eutrophic conditions in tropical rivers

This work deals with an approach for the water quality restoration with emphasis on the removal of organochlorine pesticides and eutrophic conditions in tropical rivers, causing influence on the management of the central-regional aqueduct, as a source of water supply for human consumption (4 million people) and industrial production in the states of Carabobo, Cojedes and Aragua, Venezuela, testing the phytoremediation techniques through Vetiveria zizanioides (VZ) species and coupled bioreactors, Sequencing Batch Reactor (SBR) followed by an Upflow Anaerobic Filter in Three Separate Stages (UAF-3SS). Five rivers are involved known as Chirgua, Paito Guacara, Ereigüe, and Tucutunemo, whose waters have been classified as hypereutrophic, and containing organochlorine pesticides (OCPs). As a sample, for Tucutunemo River, OCPs included to DDT (dichlorodiphenyltrichloroethane) and its isomers and DRINs (Aldrin, Endrin and Dieldrin) dissolved in water and sorbed on sediments, which were measured during the dry and rainy seasons in the period 2013 to 2016, in three monitoring stations distributed in a reach of 15 km. The results indicated that p.p′-DDT concentration dissolved in water was increased up to 10 times from rainy to dry seasons, indicating that a permanent use of it is being carried out by farmers in the agricultural activity development. Steady concentrations of the DTT isomers (e.g., p.p′-DDD and p.p′-DDE) and Aldrin isomers (e.g., Dieldrin) demonstrated that the anaerobic and aerobic biodegradation processes occurred along the river and between climatic seasons. At experimental scale, VZ hydroponic system developed over a period of 6 months for the removal of nutrients demonstrated moderately low to high removal efficiencies. With respect coupled bioreactors, each bioreactor has been experimentally tested, demonstrating satisfactory performance in Chemical Oxygen Demand (COD) removal from industrial wastewater containing recalcitrant and inhibitory substances (46%–98%), which was estimated in the influent ranging from 3500 to 5500 mg/L, evidencing that coupling of bioreactors might lead to a effluent COD complying with environmental regulations.     

Polymer nanoparticles containing essential oils: new options for mosquito control

Environmental Science and Pollution Research - Mosquitoes (Diptera: Culicidae) are vectors of important parasites and pathogens causing death, poverty and social disability worldwide. The overuse...     

Proposal to optimize ecotoxicological evaluation of wastewater treated by conventional biological and ozonation processes

A mixture of urban and hospital effluents (50 % v/v) was evaluated for ecotoxicity with an advanced bioassay battery. Mixed effluents were tested before any treatment, after biological treatment alone, and after biological treatment followed by a tertiary ozonation (15 mg O₃/L). Laying a high value on the continuance of organisms’ fitness, essential to preserve a healthy receiving ecosystem, the main objective of this study was to combine normalized bioassays with newly developed in vivo and in vitro tests in order to assess alteration of embryo development, growth and reproduction, as well as genotoxic effects in aquatic organisms exposed to complex wastewater effluents. Comparison of the bioassays sensitivity was considered. Contrary to the lack of toxicity observed with normalized ecotoxicity tests, endpoints measured on zebrafish embryos such as developmental abnormalities and genotoxicity demonstrated a residual toxicity in wastewater both after a biological treatment followed or not by a tertiary O₃ treatment. However, the ozonation step allowed to alleviate the residual endocrine disrupting potential measure in the biologically treated effluent. This study shows that normalized bioassays are not sensitive enough for the ecotoxicological evaluation of wastewaters and that there is a great need for the development of suitable sensitive bioassays in order to characterize properly the possible residual toxicity of treated effluents.     

Zero valent iron mediated degradation of the pharmaceutical diazepam

Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H₂SO₄ is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe⁰ (25 g L⁻¹) pre-treated with H₂SO₄ in the presence of EDTA (119 mg L⁻¹), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe⁰/EDTA/O₂ degradation, which evidences that OH was the main oxidizing species formed in this process.     

Inter-species differences for polychlorinated biphenyls and polybrominated diphenyl ethers in marine top predators from the Southern North Sea: Part 1. Accumulation patterns in harbour seals and harbour porpoises

Harbour porpoises (Phocoena phocoena) and harbour seals (Phoca vitulina) are two representative top predator species of the North Sea ecosystem. The median values of sum of 21 polychlorinated biphenyl (PCB) congeners and sum of 10 polybrominated diphenyl ether (PBDE) congeners were 23.1 μg/g lipid weight (lw) and 0.33 μg/g lw in blubber of harbour seals (n = 28) and 12.4 μg/g lw and 0.76 μg/g lw in blubber of harbour porpoises (n = 35), respectively. For both species, the highest PCB concentrations were observed in adult males indicating bioaccumulation. On the contrary, the highest PBDE concentrations were measured in juveniles, likely due to better-developed metabolic capacities with age in adults. A higher contribution of lower chlorinated and non-persistent congeners, such as CB 52, CB 95, CB 101, and CB 149, together with higher contributions of other PBDE congeners than BDE 47, indicated that harbour porpoises are unable to metabolize these compounds. Harbour seals showed a higher ability to metabolize PCBs and PBDEs.     

Characterization of African Dust (PM2.5) across the Atlantic Ocean during AEROSE 2004

An Aerosol and Oceanographic Science Expedition (AEROSE) on the NOAA Ship Ronald H. Brown collected PM_2.5 particles from a Saharan dust storm in March 2004. High levels of PM_2.5 (120 μg m^?3) were measured during this Saharan storm over the Atlantic Ocean. The particles were characterized for trace element content, with Al and Fe the most abundant metals. These metals were detected in high concentrations during the Saharan event and exhibited good correlations with PM_2.5, suggesting its soil origin. Other elements (Pb, Ni, Cd) did not correlate with Al and Fe, indicating their anthropogenic origin. Enrichment factor calculation conducted on these trace elements support our findings. Trace element analyses performed on particulate matter from a reference site on land in Puerto Rico (Fajardo), demonstrated similar results to those obtained in the AEROSE expedition, where high concentrations of PM_2.5 and Fe were present concomitantly with Saharan events at this station.     

Organic carbon,total nitrogen,and water-soluble ions in clouds from a tropical montane cloud forest in Puerto Rico

Chemical characterization to determine the organic and nitrogen fractions was performed on cloud water samples collected in a mountaintop site in Puerto Rico. Cloud water samples showed average concentrations of 1.09 mg L^?1 of total organic carbon (TOC), of 0.85 mg L^?1 for dissolved organic carbon (DOC) and of and 1.25 mg L^?1 for total nitrogen (TN). Concentrations of organic nitrogen (ON) changed with the origin of the air mass. Changes in their concentrations were observed during periods under the influence of African dust (AD). The ON/TN ratios were 0.26 for the clean and 0.35 for the AD periods. Average concentrations of all these species were similar to those found in remote environments with no anthropogenic contribution. In the AD period, for cloud water the concentrations of TOC were 4 times higher and TN were 3 times higher than during periods of clean air masses associated with the trade winds. These results suggest that a significant fraction of TOC and TN in cloud and rainwater is associated to airborne particulate matter present in dust. Functional groups were identified using proton nuclear magnetic resonance (¹H NMR) spectroscopy. This characterization led to the conclusion that water-soluble organic compounds in these samples are mainly aliphatic oxygenated compounds, with a small amount of aromatics. The ion chromatography results showed that the ionic species were predominantly of marine origin, for air masses with and without African dust influence, with cloud water concentrations of NO₃^? and NH₄⁺ much lower than from polluted areas in the US. An increase of such species as SO₄^2?, Cl^?, Mg²⁺, K⁺ and Ca²⁺ was seen when air masses originated from northwest Africa. The changes in the chemical composition and physical properties of clouds associated with these different types of aerosol particles could affect on cloud formation and processes.     

Chloroperoxidase-mediated transformation of highly halogenated monoaromatic compounds

Peroxidase transformations of widely distributed pollutants, tetra- and penta-chlorinated phenols and anilines, were studied using different peroxidases. Chloroperoxidase from Caldariomyces fumago was able to transform tetra- and penta-chlorinated phenols and anilines, while horseradish peroxidase, lignin peroxidase from Phanerochaete chrysosporium and versatile peroxidase from Bjerkandera adusta were able only to transform the halogenated phenols. Chloroperoxidase showed a specific activity on pentachlorophenol two orders of magnitude higher than lignin peroxidase and horseradish peroxidase, and one order of magnitude higher than versatile peroxidase. The main product from peroxidase oxidation in all cases was a polymeric and insoluble material. The insolubilization of halogenated phenols and anilines permits their removal, reduces their bioavailability, and thus reduces their environmental impact. The other minor products from the enzymatic transformation of highly chlorinated compounds were determined by mass spectrometry. Tetrachloroquinone, dimers and trimers of halogenated compounds were also identified. Chloroperoxidase was able to halogenate tetrachloroaniline to form pentachloroaniline.     

Binary mixtures of azinphos-methyl oxon and chlorpyrifos oxon produce in vitro synergistic cholinesterase inhibition in Planorbarius corneus

In this study, the cholinesterase (ChE) and carboxylesterase (CES) activities present in whole organism homogenates from Planorbarius corneus and their in vitro sensitivity to organophosphorous (OP) pesticides were studied. Firstly, a characterization of ChE and CES activities using different substrates and selective inhibitors was performed. Secondly, the effects of azinphos-methyl oxon (AZM-oxon) and chlorpyrifos oxon (CPF-oxon), the active oxygen analogs of the OP insecticides AZM and CPF, on ChE and CES activities were evaluated. Finally, it was analyzed whether binary mixtures of the pesticide oxons cause additive, antagonistic or synergistic ChE inhibition in P. corneus homogenates. The results showed that the extracts of P. corneus preferentially hydrolyzed acetylthiocholine (AcSCh) over propionylthiocholine (PrSCh) and butyrylthiocholine (BuSCh). Besides, AcSCh hydrolyzing activity was inhibited by low concentrations of BW284c51, a selective inhibitor of AChE activity, and also by high concentrations of substrate. These facts suggest the presence of a typical AChE activity in this species. However, the different dose-response curves observed with BW284c51 when using PrSCh or BuSCh instead of AcSCh suggest the presence of at least another ChE activity. This would probably correspond to an atypical BuChE. Regarding CES activity, the highest specific activity was obtained when using 2-naphthyl acetate (2-NA), followed by 1-naphthyl acetate (1-NA); p-nitrophenyl acetate (p-NPA), and p-nitrophenyl butyrate (p-NPB). The comparison of the IC(50) values revealed that, regardless of the substrate used, CES activity was approximately one order of magnitude more sensitive to AZM-oxon than ChE activity. Although ChE activity was very sensitive to CPF-oxon, CES activity measured with 1-NA, 2-NA, and p-NPA was poorly inhibited by this pesticide. In contrast, CES activity measured with p-NPB was equally sensitive to CPF-oxon than ChE activity. Several specific binary combinations of AZM-oxon and CPF-oxon caused a synergistic effect on the ChE inhibition in P. corneus homogenates. The degree of synergism tended to increase as the ratio of AZM-oxon to CPF-oxon decreased. These results suggest that synergism is likely to occur in P. corneus snails exposed in vivo to binary mixtures of the OPs AZM and CPF.     

Effects of the organic matter from swine wastewater on the adsorption and desorption of alachlor in soil

The application of swine wastewater to the soil for agricultural purposes results in the addition of total and dissolved organic matter to the soil, which may interfere with the dynamics of pesticides in the soil. The objective of this study was to evaluate the effects of the application of total and dissolved organic matter from a biodigester and a treatment lagoon of swine wastewater in the adsorption and desorption of alachlor [2-chloro-2,6-diethyl-N(methoxymethyl acetamide)]. The assay was performed by the batch equilibrium method, and the results were fitted to the Freundlich model. The curve comparison test revealed a greater adsorption of alachlor in the soil treated with swine wastewater from the biodigester. The adsorption and desorption of alachlor increased in the soils where swine wastewater was added, and hysteresis was observed in all of the treatments.