Application of SPARROW Modeling to Understanding Contaminant Fate and Transport from Uplands to Streams

Understanding spatial variability in contaminant fate and transport is critical to efficient regional water‐quality restoration. An approach to capitalize on previously calibrated spatially referenced regression (SPARROW) models to improve the understanding of contaminant fate and transport was developed and applied to the case of nitrogen in the 166,000 km² Chesapeake Bay watershed. A continuous function of four hydrogeologic, soil, and other landscape properties significant (α = 0.10) to nitrogen transport from uplands to streams was evaluated and compared among each of the more than 80,000 individual catchments (mean area, 2.1 km²) in the watershed. Budgets (including inputs, losses or net change in storage in uplands and stream corridors, and delivery to tidal waters) were also estimated for nitrogen applied to these catchments from selected upland sources. Most (81%) of such inputs are removed, retained, or otherwise processed in uplands rather than transported to surface waters. Combining SPARROW results with previous budget estimates suggests 55% of this processing is attributable to denitrification, 23% to crop or timber harvest, and 6% to volatilization. Remaining upland inputs represent a net annual increase in landscape storage in soils or biomass exceeding 10 kg per hectare in some areas. Such insights are important for planning watershed restoration and for improving future watershed models.     

Biological control of AFB1-producing Aspergillus section Flavi strains isolated from brewer's grains,alternative feed intended for swine production in Argentina

The aim of the present study was to investigate the inhibitory activity of lactic acid bacteria (LAB) isolated from brewer's grains on Aspergillus section Flavi growth and aflatoxin B₁ production. The Aspergillus strains tested were inhibited by all the LAB strains assayed. The isolates Lactobacillus brevis B20, P. pentosaceus B86, Lactococcus lactis subsp. lactis B87, L. brevis B131, and Lactobacillus sp. B144 completely suppressed the fungal growth and reduced aflatoxin B₁ production. In conclusion, LAB isolated from brewer's grains show a high inhibitory activity on fungal growth and aflatoxin biosynthesis by Aspergillus flavus and Aspergillus parasiticus. Further studies must be conducted to evaluate the success of in vitro assays under food environment conditions and to elucidate the antifungal mechanism of these strains.     

Electrochemical wastewater treatment: influence of the type of carbon and of nitrogen on the organic load removal

Boron-doped diamond (BDD) and Ti/Pt/PbO₂ anodes were utilized to perform the electrodegradation of synthetic samples containing humic acid in the presence of different organic and inorganic carbon-containing and nitrogen-containing compounds. The influence of the chloride ion in the degradation process of the different synthetic samples was also assessed. The results showed that the anodic oxidation process can efficiently degrade recalcitrant compounds such as humic acid. The presence of carbonate in solution enhances the nitrogen removal, whereas it hinders the oxidation of the organic compounds. When organic nitrogen is present, it is converted to NH₄ ⁺, which in turn is oxidized to nitrate and to volatile nitrogen compounds. Hydroxyl radicals are more prone to oxidize the organic nitrogen than the ammonium nitrogen. The presence of chloride enhances the organic matter and nitrogen removal rates, BDD being the anode material that yields the highest removals.     

Analysis of hazardous material releases due to natural hazards in the United States

Natural hazards were the cause of approximately 16,600 hazardous material (hazmat) releases reported to the National Response Center (NRC) between 1990 and 2008-three per cent of all reported hazmat releases. Rain-induced releases were most numerous (26 per cent of the total), followed by those associated with hurricanes (20 per cent), many of which resulted from major episodes in 2005 and 2008. Winds, storms or other weather-related phenomena were responsible for another 25 per cent of hazmat releases. Large releases were most frequently due to major natural disasters. For instance, hurricane-induced releases of petroleum from storage tanks account for a large fraction of the total volume of petroleum released during 'natechs' (understood here as a natural hazard and the hazardous materials release that results). Among the most commonly released chemicals were nitrogen oxides, benzene, and polychlorinated biphenyls. Three deaths, 52 injuries, and the evacuation of at least 5,000 persons were recorded as a consequence of natech events. Overall, results suggest that the number of natechs increased over the study period (1990-2008) with potential for serious human and environmental impacts.     

Megacities and Large Urban Agglomerations in the Coastal Zone: Interactions Between Atmosphere, Land, and Marine Ecosystems

Megacities are not only important drivers for socio-economic development but also sources of environmental challenges. Many megacities and large urban agglomerations are located in the coastal zone where land, atmosphere, and ocean meet, posing multiple environmental challenges which we consider here. The atmospheric flow around megacities is complicated by urban heat island effects and topographic flows and sea breezes and influences air pollution and human health. The outflow of polluted air over the ocean perturbs biogeochemical processes. Contaminant inputs can damage downstream coastal zone ecosystem function and resources including fisheries, induce harmful algal blooms and feedback to the atmosphere via marine emissions. The scale of influence of megacities in the coastal zone is hundreds to thousands of kilometers in the atmosphere and tens to hundreds of kilometers in the ocean. We list research needs to further our understanding of coastal megacities with the ultimate aim to improve their environmental management.     

Photolytic and photocatalytic degradation of quinclorac in ultrapure and paddy field water: identification of transformation products and pathways

Quinclorac (QNC) is an effective but rather persistent herbicide commonly used in rice production. This herbicide presents a mean persistence in the environment so its residues are considered of environmental relevance. However, few studies have been conducted to investigate its environmental behavior and degradation. In the present work, direct photolysis and TiO₂ photocatalysis of the target compound in ultrapure and paddy field water were investigated. After 10 h photolysis in ultrapure water, the concentration of QNC declined 26% and 54% at 250 and 700 W m⁻², respectively. However, the amount of quinclorac in paddy field water remained almost constant under the same irradiation conditions. QNC dissipated completely after 40 min of TiO₂ photocatalysis in ultrapure water, whereas 130 min were necessary to degrade 98% of the initial concentration in paddy field water.Possible QNC photolytic and photocatalytic degradation pathways are proposed after structure elucidation of the main transformation products, through liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry and exact mass measurements. Pyridine ring hydroxylation at C-9 followed by ring opening and/or oxidative dechlorination were the key steps of QNC degradation.     

Relative bioavailability to laying hens of indicator polychlorobiphenyls present in soil

Transfer of indicator polychlorobiphenyls (PCBs) from soil into hen eggs may occur in hens reared outdoor, which ingest significant amounts of soil. This transfer depends on the bioavailability of the ingested compounds. The impact of soil on the bioavailability of indicator PCBs was assessed by means by a relative bioavailability (RBA) trial, in which their deposition in egg yolk and in abdominal fat, in response to their ingestion through contaminated-soil and through spiked-oil were compared. A sandy soil (709 μg indicator PCBs kg⁻¹ dry matter) was collected in the vicinity of a former fire involving treated wood. Twenty-eight laying hens were individually housed and fed one of the seven experimental diets during 14 d. The seven experimental diets were an uncontaminated control diet, three diets in which contaminated soil was introduced at levels of 3%, 6% and 9% and three diets in which spiked oil was introduced to achieve similar levels and profile of contaminants. Yolk, abdominal fat and liver were collected at the end of exposure. Indicator PCBs were extracted by ASE (Accelerated Solvent Extraction) and analyzed by GC-HMRS. Within each ingested matrix, the concentration of indicator PCBs in yolk and in abdominal fat linearly increased with the amount of indicator PCB ingested (P < 0.001). Except for PCB 28, the slopes of the responses to soil and to oil could not be differentiated (P > 0.1). RBA estimates did not differ from 1 for all indicator PCBs except for PCB 28, for which it was 0.58-0.59. Measurements performed on liver confirm these conclusions.     

Photolysis of flumequine: identification of the major phototransformation products and toxicity measures

Direct photolysis of flumequine (FLU, 20 mg L⁻¹) in different types of water (demineralised water (DW) and synthetic seawater (SW)), was conducted in a Suntest CPS + solar simulator to evaluate its persistence and toxicity, and to identify the major phototransformation products (PTPs) generated during photolysis in DW. It was observed that FLU is susceptible to transformation when subjected to direct solar radiation. The composition of the water affects the FLU degradation kinetics, which is slower in SW. Photolytic transformation products generated during direct photolysis were identified by liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS). Fourteen PTPs generated in DW were identified. The transformation of FLU begins with the opening of the heterocyclic ring by oxidation of the double bond. Loss of the fluorine atom and the hydroxylation of the aromatic ring also appear as the majority, especially in the early stages. Comparative acute toxicity evaluation by Vibrio fischeri and Daphnia magna bioassays was performed for the first and last irradiated solutions in both matrices studied. These bioassays demonstrated that in the SW matrix, the most persistent PTPs are highly toxic to D. magna but less so to V. fischeri.     

Analytical improvements of hybrid LC-MS/MS techniques for the efficient evaluation of emerging contaminants in river waters: a case study of the Henares River (Madrid, Spain)

Purpose  

Instrumental capabilities and software tools of modern hybrid mass spectrometry (MS) instruments such as high-resolution mass spectrometry (HRMS), quadrupole time-of-flight (QTOF), and quadrupole linear ion trap (QLIT) were experimentally investigated for the study of emerging contaminants in Henares River water samples.