Occurrence and distribution of six selected endocrine disrupting compounds in surface- and groundwaters of the Romagna area (North Italy)

Environmental Science and Pollution Research - Endocrine disrupting compounds (EDCs) are a wide group of contaminants of emerging concern known to be harmful for organisms. The aim of the study was...     

Sediments as a sink for UV filters and benzotriazoles: the case study of Upper Iguaçu watershed,Curitiba (Brazil)

Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g⁻¹ dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.

     

Emission factors of particulate matter,polycyclic aromatic hydrocarbons,and levoglucosan from wood combustion in south-central Chile

In south-central Chile, wood stoves have been identified as an important source of air pollution in populated areas. Eucalyptus (Eucalyptus globulus), Chilean oak (Nothofagus oblique), and mimosa (Acacia dealbata) were burned in a single-chamber slow-combustion wood stove at a controlled testing facility located at the University of Concepción, Chile. In each experiment, 2.7–3.1 kg of firewood were combusted while continuously monitoring temperature, exhaust gases, burn rate, and collecting particulate matter samples in Teflon filters under isokinetic conditions for polycyclic aromatic hydrocarbon and levoglucosan analyses. Mean particulate matter emission factors were 2.03, 4.06, and 3.84 g/kg dry wood for eucalyptus, oak, and mimosa, respectively. The emission factors were inversely correlated with combustion efficiency. The mean emission factors of the sums of 12 polycyclic aromatic hydrocarbons in particle phases were 1472.5, 2134.0, and 747.5 μg/kg for eucalyptus, oak, and mimosa, respectively. Fluoranthene, pyrene, benzo[a]anthracene, and chrysene were present in the particle phase in higher proportions compared with other polycyclic aromatic hydrocarbons that were analyzed. Mean levoglucosan emission factors were 854.9, 202.3, and 328.0 mg/kg for eucalyptus, oak, and mimosa, respectively. Since the emissions of particulate matter and other pollutants were inversely correlated with combustion efficiency, implementing more efficient technologies would help to reduce air pollutant emissions from wood combustion.

Implications: Residential wood burning has been identified as a significant source of air pollution in populated areas. Local wood species are combusted for home cooking and heating, which releases several toxic air pollutants, including particulate matter, carbon monoxide, and polycyclic aromatic hydrocarbons. Air pollutant emissions depend on the type of wood and the technology and operational conditions of the wood stove. A better understanding of emissions from local wood species and wood stove performance would help to identify better biomass fuels and wood stove technologies in order to reduce air pollution from residential wood burning.     

The influence of light exposure,water quality and vegetation on the removal of sulfonamides and tetracyclines: A laboratory-scale study

The effect of aquatic vegetation (Spyrogira sp. and Zannichellia palustris), light exposure and water quality (secondary-treated wastewater vs. ultrapure water) on the removal efficiency of six antibiotics (sulfonamides and tetracyclines) is studied in laboratory-scale reactors. After 20 d of treatment, 3–59% of sulfonamides were eliminated in the reactors exposed to light. Removal was about 10% in unplanted reactors in darkness. The elimination of tetracycline (TC) and oxytetracycline (OTC) ranged between 83% and 97% in both planted and unplanted reactors. However, in dark unplanted reactors, OTC was largely removed (88%) while only 15% of TC was eliminated. These results suggest that TC was mainly removed by photodegradation whereas biodegradation or hydrolysis process seems to be significant processes for OTC. Sulfonamides were mainly eliminated by biodegradation or indirect photodegradation processes. Pseudo-first order kinetics removal rates ranged from 0.003 and 0.007 d^?1 for Sulfamethazine and TC in the covered control reactors to 0.13 and 0.21 d^?1 for TC and OTC in the uncovered control reactors, with half-lives from 3 to 350 d. A TC photodegradation product was tentatively identified in uncovered reactors. This study highlights the important role played by light exposure in the elimination of antibiotics in polishing ponds.     

Removal of sulfamethoxazole and sulfapyridine by carbon nanotubes in fixed-bed columns

Sulfamethoxazole (SMX) and sulfapyridine (SPY), two representative sulfonamide antibiotics, have gained increasing attention because of the ecological risks these substances pose to plants, animals, and humans. This work systematically investigated the removal of SMX and SPY by carbon nanotubes (CNTs) in fixed-bed columns under a broad range of conditions including: CNT incorporation method, solution pH, bed depth, adsorbent dosage, adsorbate initial concentration, and flow rate. Fixed-bed experiments showed that pH is a key factor that affects the adsorption capacity of antibiotics to CNTs. The Bed Depth Service Time model describes well the relationship between service time and bed depth and can be used to design appropriate column parameters. During fixed-bed regeneration, small amounts of SMX (3%) and SPY (9%) were irreversibly bonded to the CNT/sand porous media, thus reducing the column capacity for subsequent reuse from 67.9 to 50.4 mg g^?1 for SMX and from 91.9 to 72.9 mg g^?1 for SPY. The reduced column capacity resulted from the decrease in available adsorption sites and resulting repulsion (i.e., blocking) of incoming antibiotics from those previously adsorbed. Findings from this study demonstrate that fixed-bed columns packed with CNTs can be efficiently used and regenerated to remove antibiotics from water.     

Phytoavailability and extractability of potassium,magnesium and manganese in calcareous soil amended with olive oil wastewater

Abstract

Land disposal of olive oil wastewater using it as a soil amendment requires a knowledge of the effects that its application may produce on the status of the mineral nutrients in the plant‐soil system. A pot experiment using calcareous soil was performed in a growth chamber to examine the effects of olive oil wastewater on the availability and postharvest soil extractability of K, Mg and Mn. The experiment included 6 treatments: two rates of olive oil wastewater, two mineral fertilizer treatments containing K (which supplied K in amounts equivalent to the K supplied by the olive oil wastewater treatments), a K‐free mineral fertilizer treatment, and a control. The pots were sown with ryegrass as the test plant, harvesting 3 times at intervals of one month. Olive oil wastewater has demonstrated a considerable capacity for supplying K that can be assimilated by the plant, tending in fact to surpass the mineral potassium fertilizer tested. The application of olive oil wastewater tends to reduce the concentration of Mg in the plant, similarly to the effect of adding mineral potassium fertilizer. An enhancement of Mn availability takes place in the soil amended with olive oil wastewater, which on occasion has produced Mn concentrations in plant that could be considered phytotoxic or at least excessive. After harvesting, we observed an increase in the amount of exchangeable K in soil with added industrial wastewater. However, these increases are lower than those in soil treated with mineral potassium fertilizer. The levels of exchangeable, carbonate‐bound, organic‐bound and residual Mg in soil were higher in treatments incorporating olive oil wastewater than in those with added mineral K, with the opposite tendency occurring in the amount of Fe‐Mn oxides‐bound Mg in soil. Treatments based on olive oil wastewater, especially in high doses, increased the amount of exchangeable and carbonate‐bound Mn in soil, in comparison with treatments adding mineral fertilizers with or without K. In contrast, the addition of industrial wastewater caused a drop in the amount of Fe‐Mn oxides‐bound and organic‐bound Mn in soil.     

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N ², N ⁴-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Effect of phenobarbital and polychlorinated biphenyls on the toxicity and disposition of 1,2,4,5‐tetrachlorobenzene in the rat

Soil avoidance by earthworms has been generally considered a relevant and sensitive endpoint for assessing soil contamination by xenobiotics. However, when pesticide ecotoxicological assessment is concerned, the sensitivity of the recently standardized avoidance assay has been questioned. We hypothesized that this controversy may be due to the specific pesticide mode of action of the chemicals used rather than reveal inconsistencies in the test feasibility, i.e. provided that no pesticides interfering with neuronal pathways are tested, this bioassay should keep expected high levels of sensitivity. In this study, the avoidance behaviour of the earthworm Eisenia andrei under exposure to the carbamate insecticide methomyl [S-methyl N-(methylcarbamoyloxy)thioacetimidate] was linked to the corresponding acetylcholinesterase (AChE) inhibition. Significant AChE inhibition occurred at lower concentrations (from 0.86 mg Kg^?1 onwards) than significant avoidance of spiked soil (from 5.62 mg Kg^?1 onwards). This indicates that assessments regarding pesticides that have neurotoxic activity may be biased if behavioral endpoints are selected. Despite theoretical hypothesis that have been raised, this should be the first study providing preliminary experimental evidence on such a link between avoidance behavior and neuronal impairment levels in earthworms. Further studies are ongoing that should refine conclusions of this study.     

Greenhouse gas emissions from the waste sector in Argentina in business-as-usual and mitigation scenarios

The objective of this work was the application of 2006 Intergovernmental Panel on Climate Change (IPCC) Guidelines for the estimation of methane and nitrous oxide emissions from the waste sector in Argentina as a preliminary exercise for greenhouse gas (GHG) inventory development and to compare with previous inventories based on 1996 IPCC Guidelines. Emissions projections to 2030 were evaluated under two scenarios—business as usual (BAU), and mitigation—and the calculations were done by using the ad hoc developed IPCC software. According to local activity data, in the business-as-usual scenario, methane emissions from solid waste disposal will increase by 73% by 2030 with respect to the emissions of year 2000. In the mitigation scenario, based on the recorded trend of methane captured in landfills, a decrease of 50% from the BAU scenario should be achieved by 2030. In the BAU scenario, GHG emissions from domestic wastewater will increase 63% from 2000 to 2030. Methane emissions from industrial wastewater, calculated from activity data of dairy, swine, slaughterhouse, citric, sugar, and wine sectors, will increase by 58% from 2000 to 2030 while methane emissions from domestic will increase 74% in the same period. Results show that GHG emissions calculated from 2006 IPCC Guidelines resulted in lower levels than those reported in previous national inventories for solid waste disposal and domestic wastewater categories, while levels were 18% higher for industrial wastewater.

Implications: The implementation of the 2006 IPCC Guidelines for National Greenhouse Inventories is now considering by the UNFCCC for non-Annex I countries in order to enhance the compilation of inventories based on comparable good practice methods. This work constitutes the first GHG emissions estimation from the waste sector of Argentina applying the 2006 IPCC Guidelines and the ad doc developed software. It will contribute to identifying the main differences between the models applied in the estimation of methane emissions on the key categories of waste emission sources and to comparing results with previous inventories based on 1996 IPCC Guidelines.     

Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.