Hemolysis,Fish Mortality,and LC-ESI-MS of Cultured Crude and Fractionated Golden Alga (Prymnesium parvum)1

Schug, Kevin A., Theodore R. Skingel, Sandra E. Spencer, Carlos A. Serrano, Cuong Q. Le, Christopher A. Schug, Theodore W. Valenti, Jr., Bryan W. Brooks, Laura D. Mydlarz, and James P. Grover, 2010. Hemolysis, Fish Mortality, and LC-ESI-MS of Cultured Crude and Fractionated Golden Alga (Prymnesium parvum). Journal of the American Water Resources Association (JAWRA) 46(1):33-44. DOI: 10.1111/j.1752-1688.2009.00389.x Abstract: Erythrocyte lysis and fish mortality assays, in combination with high performance liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) analysis, were investigated for bioassay-guided fractionation of cultured golden alga (Prymnesium parvum). Intracellular constituents from isolated cell pellets and extracellular supernatant growth medium were fractionated by a variety of common separation modes, including reversed phase and normal phase solid phase extraction step fractionation procedures. For reversed phase fractionation of extracellular growth medium, one fraction was obtained that displayed hemolytic activity and adversely affected fish survival. Effective dose concentrations for this sample were similar in both assays and the LC-ESI-MS analysis of the fraction showed a number of mass spectral signals which were distinct to this fraction. Fractions obtained from separation of an ethanol extract of the lyophilized cell pellet provided one sample that was highly hemolytic, but not toxic to fish. Discrepancies such as this, along with notable fish behavioral responses from other nonhemolytic cell pellet fractions, problems with the use of unbonded silica gel for fractionation, and misleading mass spectral signatures are interesting in the context of our current understanding of P. parvum toxicity and remain to be investigated further. This work provides an account of ongoing research aimed toward comprehensive elucidation of toxic constituents produced by golden alga for the purpose of providing a better understanding and means to potentially remediate the ecological impact of this harmful bloom organism.     

In vitro biological effects of airborne PM₂.₅ and PM₁₀ from a semi-desert city on the Mexico-US border

Compelling evidence indicates that exposure to urban airborne particulate matter (PM) affects health. However, how PM components interact with PM-size to cause adverse health effects needs elucidation, especially when considering soil and anthropogenic sources. We studied PM from Mexicali, Mexico, where soil particles contribute importantly to air pollution, expecting to differentiate in vitro effects related to PM-size and composition. PM samples with mean aerodynamic diameters ≤2.5μm (PM(2.5)) and ≤10μm (PM(10)) were collected in Mexicali (October 2005-March 2006) from a semi-urban (expected larger participation of soil sources) and an urban (predominately combustion sources) site. Samples were pooled by site and size, analyzed for elemental composition (particle-induced X-ray emission) and tested in vitro for: induction of human erythrocytes membrane disruption (hemolysis) (colorimetrically); inhibition of cell proliferation (ICP) (crystal violet) and TNFα/IL-6 secretion (ELISA) using J774.A1 murine monocytic cells; and DNA degradation using Balb/c3T3 cell naked DNA (electrophoretically). Results of PM elemental composition principal component analysis were used in associating cellular effects. Sixteen elements identified in PM grouped in two principal components: Component(1) (C(1)): Mg, Al, Si, P, Cl, K, Ca, Ti, V, Cr, Fe, and Component(2) (C(2)): Cu, Zn. Hemolysis was predominately induced by semi-urban-PM(10) (p<0.05) and was associated with urban-PM(10)C(1) (r=0.62, p=0.003). Major ICP resulted with semi-urban PM(2.5) (p<0.05). TNFα was mainly induced by urban samples regardless of size (p<0.05) and associated with urban-PM(2.5)C(2) (r=0.48, p=0.02). Both PM(10) samples induced highest DNA degradation (p<0.05), regardless of location. We conclude that PM-size and PM-related soil or anthropogenic elements trigger specific biological-response patterns.     

Combined effects of soil moisture and carbaryl to earthworms and plants: simulation of flood and drought scenarios

Studying tolerance limits in organisms exposed to climatic variations is key to understanding effects on behaviour and physiology. The presence of pollutants may influence these tolerance limits, by altering the toxicity or bioavailability of the chemical. In this work, the plant species Brassica rapa and Triticum aestivum and the earthworm Eisenia andrei were exposed to different levels of soil moisture and carbaryl, as natural and chemical stressors, respectively. Both stress factors were tested individually, as well as in combination. Acute and chronic tests were performed and results were discussed in order to evaluate the responses of organisms to the combination of stressors. When possible, data was fitted to widely employed models for describing chemical mixture responses. Synergistic interactions were observed in earthworms exposed to carbaryl and drought conditions, while antagonistic interactions were more representative for plants, especially in relation to biomass loss under flood-simulation conditions.     

Characterization of municipal solid waste from the main landfills of Havana city

The city of Havana, the political, administrative and cultural centre of Cuba, is also the centre of many of the economic activities of the nation: industries, services, scientific research and tourism. All of these activities contribute to the generation of municipal solid waste (MSW), which also impact other Cuban cities. Inadequate handling of waste and the lack of appropriate and efficient solutions for its final disposal and treatment increase the risk and possibility of contamination. The main difficulty in the development of a system of management of MSW lies in the lack of knowledge of the chemical composition of the waste that is generated in the country as a whole, and especially in Havana, where solid waste management decisions are made. The present study characterizes MSW in Havana city during 2004. The Calle 100, Guanabacoa and Ocho Vías landfills were selected for physical-chemical characterization of MSW, as they are the three biggest landfills in the city. A total of 16 indicators were measured, and weather conditions were recorded. As a result, the necessary information regarding the physical-chemical composition of the MSW became available for the first time in Cuba. The information is essential for making decisions regarding the management of waste and constitutes a valuable contribution to the Study on Integrated Management Plan of MSW in Havana.     

Renewable energy subsidies versus carbon capture and sequestration support

We propose an equilibrium model where final-goods production uses labor and energy, and energy production uses non-polluting Renewable Energy Sources (RES) and polluting fossil fuels. Our goal is to compare two alternative Green Tax Reforms (GTRs). In one of the GTRs, carbon tax revenues are used to support Carbon Capture and Sequestration (CCS) activities. In the other GTR, tax revenues are used to subsidize RES. The comparison between the two GTRs is focused on three indicators: output per worker, energy intensity and the ratio of renewables over non-renewables. Results show that, in theory, the GTR with the RES subsidy could benefit both the economy and the environment if resource substitution was strong enough. The GTR with CCS support necessarily decreases output since abatement only partially alleviates the tax burden. The empirical simulation indicates that, for most tax values, both GTRs imply an economic slowdown but benefit the environment. The GTR with RES subsidies appears to be preferable than the alternative one, especially for lower tax levels.     

Water Footprint of 65 Mid‐ to Large‐Sized U.S. Cities and Their Metropolitan Areas

Conventional indicators of water use for urban areas account primarily for direct water use. In contrast, our objective here is to employ the water footprint (WF) concept and methodology to include the virtual or indirect water use to assess the production‐side and consumption‐side WF of 65 United States (U.S.) cities. The 65 cities include the largest metropolitan areas and some of the major mid‐sized cities in the U.S. We use metropolitan areas to define our city boundaries as this is the native spatial resolution of the main datasets used. To estimate the urban WFs, we integrated large and disparate datasets, including commodity flow (agricultural, livestock, and industrial commodities), water use, and socioeconomic data. By analyzing the estimated WF values, we found indirect water use accounts on average for 66% of the WF of consumption. We found some cities are net virtual water exporters (11 of 65) because they rely heavily on direct water uses or are heavy producers of industrial commodities. Also, WF patterns vary widely across the U.S. but regional patterns seem to emerge. For example, the dense cities of the U.S. northeast megaregion have a significantly low per capita WF relative to the other cities, while cities in the Gulf Coast megaregion have a significantly higher industrial WF of production and consumption. Furthermore, there is inequality in the WF of consumption where a few cities account for a disproportionate share of the total U.S. urban water uses.     

Health risks of environmental exposure to metals and herbicides in the Pardo River,Brazil

Mixture of metals and herbicides in rivers may pose relevant risks for the health of surrounding communities. Humans may be exposed to river pollution through intake of contaminated water and fish, as well as irrigated agricultural products. The aim of this study was to assess the human health risks of environmental exposure to metals and herbicides through water and fish intake in the Pardo River. Metals (Al, As, Be, Cd, Cr, Cu, Pb, Mn, Hg, Ni, Tl, Sn, V, and Zn) were analyzed in river water and in edible fish. Herbicides (ametryn, atrazine, diuron, hexazinone, simazine, and tebuthiuron) were analyzed in river water. Seasonal variances were also studied. Aluminum, Cd, Cu, Mn, Pb, and Zn levels in river water were higher than the USEPA benchmarks. Non-carcinogenic risks due to pollutants mixture exposure were above the limit, and carcinogenic risks of As exposure were >10^?6 in the sampling points during the rainy season. Metal levels in fish were lower than the Brazilian legislation and do not pose a threat to public health. Herbicides were detected in four sampling points, with atrazine concentrations (range 0.16–0.32 μg/L) below the Brazilian standard (2.0 μg/L), but above the European Union standard (0.1 μg/L). Considering the water supply needs of cities located in the Pardo River Basin and the persistence of metals and herbicides, the present study indicated that there was a seasonal influence on non-carcinogenic and carcinogenic risks to human health, especially in the rainy season. Studies for water treatment plants implantation should consider the risks of exposure to persistent substances, in order to protect the population.     

Occurrence and removal of pharmaceuticals in wastewater treatment plants at the Spanish Mediterranean area of Valencia

A survey on the presence of pharmaceuticals in urban wastewater of a Spanish Mediterranean area (Castellon province) was carried out. The scope of the study included a wide variety of pharmaceuticals belonging to different therapeutical classes. For this purpose, 112 samples, including influent and effluent wastewater, from different conventional wastewater treatment plants were collected. Two monitoring programmes were carried out along several seasons. The first was in June 2008 and January 2009, and the second in April and October 2009. During the first monitoring, the occurrence of 20 analytes in 84 urban wastewater samples (influent and effluent) was studied. The selection of these pharmaceuticals was mainly based on consumption. From these, 17 compounds were detected in the samples, with analgesics and anti-inflammatories, cholesterol lowering statin drugs and lipid regulators being the most frequently detected groups. 4-Aminoantipyrine, bezafibrate, diclofenac, gemfibrozil, ketoprofen, naproxen and venlafaxine were the compounds most frequently found. In the highlight of these results, the number of analytes was increased up to around 50. A lot of antibiotic compounds were added to the target list as they were considered “priority pharmaceuticals” due to their more potential hazardous effects in the aquatic environment. Data obtained during the second monitoring programme (spring and autumn) corroborated the results from the first one (summer and winter). Analgesics and anti-inflammatories, lipid regulators together with quinolone and macrolide antibiotics were the most abundant pharmaceuticals. Similar median concentrations were found over the year and seasonal variation was not clearly observed. The removal efficiency of pharmaceuticals in the wastewater treatment plants was roughly evaluated. Our results indicated that elimination of most of the selected compounds occurred during the treatment process of influent wastewater, although it was incomplete.     

Sonophotocatalytic degradation of alazine and gesaprim commercial herbicides in TiO2 slurry

The photocatalytic degradation of alazine and gesaprim commercial herbicides was carried out in aqueous TiO(2) suspensions under UV light (15W, 352 nm). Degradation of these herbicides was also observed by the combined effects of photocatalysis with sonolysis (sonophotocatalysis) using an ultrasound source of 20kHz. Degradation profiles were recorded by measuring the concentration of the active compounds present in the alazine (alachlor and atrazine) and gesaprim (atrazine) by HPLC as a function of irradiation time (sound and/or light). Over 90% of the active component in the gesaprim was abated and those in alazine were completely degraded. The content of total organic carbon and chemical oxygen demand was also monitored. Mineralization of the commercial herbicides was achieved. Over 80% of chemical oxygen demand abatement was attained for both herbicides with sonophotocatalysis at 150 min of irradiation time. The photocatalytic degradation of the herbicides followed a pseudo-first order kinetics and their rate constant was increased by the combined effects of sonolysis.     

Chemical characterisation of particulate matter in urban transport modes

Traffic is a main source of air pollutants in urban areas and consequently daily peak exposures tend to occur during commuting. Personal exposure to particulate matter (PM) was monitored while cycling and travelling by bus, car and metro along an assigned route in Lisbon (Portugal), focusing on PM2.5 and PM10 (PM with aerodynamic diameter <2.5 and 10 µm, respectively) mass concentrations and their chemical composition. In vehicles, the indoor-outdoor interplay was also evaluated. The PM2.5 mean concentrations were 28?±?5, 31?±?9, 34?±?9 and 38?±?21?µg/m³ for bus, bicycle, car and metro modes, respectively. Black carbon concentrations when travelling by car were 1.4 to 2.0 times higher than in the other transport modes due to the closer proximity to exhaust emissions. There are marked differences in PM chemical composition depending on transport mode. In particular, Fe was the most abundant component of metro PM, derived from abrasion of rail-wheel-brake interfaces. Enhanced concentrations of Zn and Cu in cars and buses were related with brake and tyre wear particles, which can penetrate into the vehicles. In the motorised transport modes, Fe, Zn, Cu, Ni and K were correlated, evidencing their common traffic-related source. On average, the highest inhaled dose of PM2.5 was observed while cycling (55 µg), and the lowest in car travels (17 µg). Cyclists inhaled higher doses of PM2.5 due to both higher inhalation rates and longer journey times, with a clear enrichment in mineral elements. The presented results evidence the importance of considering the transport mode in exposure assessment studies.