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.     

Assessing disproportionate costs to achieve good ecological status of water bodies in a Mediterranean river basin

Water management is becoming increasingly important as the demand for water grows, diversifies, and includes more complex environmental concerns. The Water Framework Directive (WFD) seeks to achieve a good ecological status for all European Community water bodies by 2015. To achieve this objective, economic consideration of water management must be given to all decision-making processes. Exemption (time or level of stringency) from the objectives of the EU Directive can be justified by proving that the cost of implementing measures is disproportionate to the benefits. This paper addresses the issue of disproportionate costs through a cost-benefit analysis (CBA). To predict the costs, the function costs method is used. The quantification of environmental benefits is more complex, because they are not determined by the market. As an alternative to stated preference methods, we use the distance function approach to estimate the environmental benefits of improving water quality. We then apply this methodological approach to a Mediterranean River Basin in Spain. The results show that the achievement of good status could not be rejected based on the criterion of disproportionate costs in this river basin. This paper illustrates that CBA is a useful tool to inform policy and decision making. Furthermore, it is shown that economics, particularly the valuation of environmental benefits, plays a crucial role in fulfilling the environmental objectives of the WFD.     

Saline irrigation and Zn amendment effect on Cd phytoavailability to Swiss chard (Beta vulgaris L.) grown on a long-term amended agricultural soil: a human risk assessment

Crops, particularly in the Northeast region of Mexico, have to cope with increasing soil salinization due to irrigation. Chloride (Cl^?) concentration has been strongly related to enhance cadmium (Cd) uptake by plants due to increased solubility in the soil solution. The effect of irrigation with slightly saline water from a local well was evaluated in this work on the accumulation and translocation of Cd in Swiss chard (Beta vulgaris L.) grown in soil historically amended with stabilized sewage sludge under a regime of phosphorus and zinc fertilization. A factorial pot experiment was conducted with two phosphate fertilizer levels (PF, 0 and 80 kg ha^?1 dry soil, respectively), two Zn levels (0 and 7 kg ha^?1 dry soil), and two sources of water for irrigation deionized water (DW) and slightly saline well water (WW) from an agricultural site. Additionally, a human risk assessment for Cd ingestion from plants was assessed. Results showed that Cl^? salinity in the WW effectively mobilized soil Cd and increased its phytoavailability. A higher level of Cd was found in roots (46.41 mg kg^?1) compared to shoots (10.75 mg kg^?1). Although the total content of Cd in the edible parts of the Swiss chard irrigated with WW exceeded permissible recommended consumption limit, bioavailable cadmium in the aboveground parts of the plant in relation to the total cadmium content was in the range from 8 to 32 %. Therefore, human health risks might be overestimated when the total concentration is taken into account.     

Leaching of potential hazardous elements of coal cleaning rejects

The geochemical characteristics of coal cleaning rejects (CCR) in Santa Catarina State, Brazil, were investigated. Around 3.5 million ton/ year of coal waste are dumped in Santa Catarina State. Coal beneficiation by froth flotation results in large amounts of CCR composed of coaly and mineral matter, the latter characterised by the occurrence of sulphide minerals and a broad array of leachable elements. The total and leachable contents of more than 60 elements were analysed. Atmospheric exposure promotes sulphide oxidation that releases substantial sulphate loads as well as Ca^2?+?, K^?+?, Mg^2?+?, Cl^??? and Al^3?+?. The metals with the most severe discharges were Zn, Cu, Mn, Co, Ni and Cd. Most trace pollutants in the CCR displayed a marked pH-dependent solubility, being immobile in near-neutral samples. The results highlight the complex interactions among mineral matter solubility, pH and the leaching of potentially hazardous elements.     

Non-controlled biogenic emissions to the atmosphere from Lazareto landfill, Tenerife, Canary Islands

GOAL, SCOPE AND BACKGROUND: [corrected] Historically, landfills have been the simplest form of eliminating urban solid waste with the minimum cost. They have been the most usual method for discarding solid waste. However, landfills are considered authentic biochemical reactors that introduce large amounts of contaminants into the environment in the form of gas and leachates. The dynamics of generation and the movement of gas in landfills depend on the input and output parameters, as well as on the structure of the landfill and the kind of waste. The input parameters include water introduced through natural or artificial processes, the characteristics of the urban solid waste, and the input of atmospheric air. The main output parameters for these biochemical reactors include the gases and the leachates that are potentially pollutants for the environment. Control systems are designed and installed to minimize the impact on the environment. However, these systems are not perfect and a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as Non-controlled emission. In this paper, the results of the Non-controlled biogenic gas emissions from the Lazareto landfill in Tenerife, Canary Islands, are presented. The purpose of this study was to evaluate the concentration of CH4 and CO2 in the soil gas of the landfill cover, the CH4 and CO2 efflux from the surface of the landfill and, finally, to compare these parameters with other similar landfills. In this way, a better understanding of the process that controls biogenic gas emissions in landfills is expected. METHODS: A Non-controlled biogenic gas emission survey of 281 sampling sites was carried out during February and March, 2002. The sampling sites were selected in order to obtain a well-distributed sampling grid. Surface landfill CO2 efflux measurements were carried out at each sampling site on the surface landfill together with soil gas collection and ground temperatures at a depth of 30-40 cm.The CH4 efflux was computed from CO2 efflux and from the ratio CH4/CO2 in the soil gas. Soil gas samples were collected at a depth of 30-40 cm using a metallic probe and 20 cc hypodermic syringes, and later stored in evacuated 10 cc vacutainers for laboratory analysis of bulk composition. The gas sample was introduced in a vacutainer filled with deionized water and displacing the water until the vacutainer was filled with the gas sample in order to avoid air contamination from entering. The surface landfill temperature of the landfill was measured at a depth of 40 cm using a digital thermometer type OMEGA 871A. Landfill gases, CO2 and CH4, were analyzed within 24 hours using a double channel VARIAN micro-GC QUAD CP-2002P, with a 10 meter PORAPLOT-Q column, a TCD detector, and He as a carrier gas. The analysis temperature was 40 degrees C and the injection time was 10 msec. Surface landfill CO2 efflux measurements were performed using a portable NDIR spectrophotometer Licor-800 according to the accumulation chamber method (Chiodini et al. 1996). The data treatment, aimed at drawing the flux map and computing the total gas output, was based on the application of stochastic simulation algorithms provided by the GSLIB program (Deutsch and Journel 1998). RESULTS: Diffuse CH4 and CO2 efflux values range from negligible values up to 7,148 and 30,573 g m(-2) d(-1), respectively. The spatial distribution of the concentration and efflux of CO2, CH4 and soil temperature, show three areas of maximum activity in the landfill, suggesting a non-uniform pattern of diffuse degassing. This correlation between high emissions and concentration of CO2, CH4 and soil temperatures suggests that the areas of higher microbial activity and exothermic reactions are releasing CO2 and CH4 to the atmosphere from the landfill. Taking into consideration the spatial distribution of the CO2 and CH4 efflux values as well as the extension of the landfill, the Non-controlled emission of CO2 and CH4 to the atmosphere by the Lazareto's landfill are of 167 +/- 13.3 and 16 +/- 2.5 t d(-1), respectively. DISCUSSION: The patterns of gas flow within the landfill seem to be affected by boundary materials at the sides. The basalt layers have a low permeability and the gas flow in these areas is extensive. In this area, where a basalt layer does not exist, the flow gas diffuses toward the sea and the flux emissions at the landfill surface are lower. This behavior reflects the possible dissolution of gases into water and the deflection of gases towards the surface at the basalt boundary. The proximity to the sea, the installation of a palm tree garden and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. The introduction of sea water into the landfill and the type of boundary could be defining the superficial gas discharges. CONCLUSIONS: Results from this study indicate that the spatial distribution of Non-controlled emission of CO2 and CH4 at the Lazareto's landfill shows a non-uniform pattern of diffuse degassing. The northeast, central and northwest areas of the Lazareto's landfill are the three areas of high emissions and concentration of CO2 and CH4, and high temperatures. The correlation between high emissions and the concentration of CO2, CH4, and the high temperatures suggest that the areas of higher microbial activity and exothermic reactions are releasing more CO2 and CH4 to the atmosphere from the landfill. A high concentration of CO2 is probably due to the presence of methanotrophic bacteria in the soil atmosphere of the landfill. Patterns of gas flow within the landfill seem to be affected by boundary materials (basalt layers) of low permeability, and side boundaries of the flux emissions at the surface are higher. At the sides of seawater and sediment boundaries, flux emissions at the landfill surface are lower. This behavior reflects a possible dissolution of gases into the water and the deflection of gases towards the surface at the basalt boundary. With this study, we can compare the data obtained in this landfill with other landfills and observe the different levels of emission. The proximity to the sea and the installation of the palm tree garden palms and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. Many landfills worldwide located in similar settings could experience similar gas production processes. RECOMMENDATIONS AND PERSPECTIVES: The need for investigating and monitoring sea water and sediment quality in these landfills is advisable. Concentrations and fluxes of contaminants and their impact in the area should be assessed. With this study we can compare the data obtained in these landfills with other landfills and observe the different levels of emission.     

Effects of the toxic dinoflagellate <Emphasis Type="Italic">Gymnodinium catenatum</Emphasis> on uptake and fate of paralytic shellfish poisons in the Pacific giant lions-paw scallop <Emphasis Type="Italic">Nodipecten subnodosus</Emphasis>

Juvenile Pacific giant lions-paw scallops Nodipecten subnodosus were fed the toxic dinoflagellate Gymnodinium catenatum, a producer of paralytic shellfish poison (PSP), supplied with Isochrysis galbana (a nontoxic microalgae). Short-term (<24 h) experiments were performed to determine clearance and ingestion rates of G. catenatum. Kinetics of PSP was examined in longer-term experiments (>2 days). At high food concentrations, juvenile scallops showed production of pseudofeces, partial shell valve closure, and reduction in feeding. According to HPLC analysis, the only toxins present in the dinoflagellate G. catenatum and in the scallops were the gonyautoxins (GTXs), except in the labial palps and digestive gland, where trace amounts of saxitoxin (STX) were present in scallops. These tissues could play an important role in toxin biotransformation. The ranking of toxin concentration in tissues was: digestive gland > labial palps > intestine > gills > mantle > adductor muscle, where the total contribution of viscera was more than 80% of the total toxin body burden. Juvenile scallops exhibited no apparent detrimental physiological responses during the long-term feeding experiment. The dinoflagellate may contribute nutrients to the scallop, in addition to the microalgae I. galbana. The dinoflagellate may enhance cell uptake and byssus production. Once PSP accumulated during the first 12 days, it was slowly eliminated. The limited capacity for accumulating toxins in the adductor muscle favors domestic marketing of scallops.     

Temperature and air velocity effects on ethanol emission from corn silage with the characteristics of an exposed silo face

Volatile organic compounds (VOCs) from agricultural sources are believed to be an important contributor to tropospheric ozone in some locations. Recent research suggests that silage is a major source of VOCs emitted from agriculture, but only limited data exist on silage emissions. Ethanol is the most abundant VOC emitted from corn silage; therefore, ethanol was used as a representative compound to characterize the pattern of emission over time and to quantify the effect of air velocity and temperature on emission rate. Ethanol emission was measured from corn silage samples removed intact from a bunker silo. Emission rate was monitored over 12 h for a range in air velocity (0.05, 0.5, and 5 m s^?1) and temperature (5, 20, and 35 °C) using a wind tunnel system. Ethanol flux ranged from 0.47 to 210 g m^?2 h^?1 and 12 h cumulative emission ranged from 8.5 to 260 g m^?2. Ethanol flux was highly dependent on exposure time, declining rapidly over the first hour and then continuing to decline more slowly over the duration of the 12 h trials. The 12 h cumulative emission increased by a factor of three with a 30 °C increase in temperature and by a factor of nine with a 100-fold increase in air velocity. Effects of air velocity, temperature, and air-filled porosity were generally consistent with a conceptual model of VOC emission from silage. Exposure duration, temperature, and air velocity should be taken into consideration when measuring emission rates of VOCs from silage, so emission rate data obtained from studies that utilize low air flow methods are not likely representative of field conditions.     

Ethanol emission from loose corn silage and exposed silage particles

Silage on dairy farms has been identified as a major source of volatile organic compound (VOC) emissions. However, rates of VOC emission from silage are not accurately known. In this work, we measured ethanol (a dominant silage VOC) emission from loose corn silage and exposed corn silage particles using wind tunnel systems. Flux of ethanol was highest immediately after exposing loose silage samples to moving air (as high as 220 g m^?2 h^?1) and declined by as much as 76-fold over 12 h as ethanol was depleted from samples. Emission rate and cumulative 12 h emission increased with temperature, silage permeability, exposed surface area, and air velocity over silage samples. These responses suggest that VOC emission from silage on farms is sensitive to climate and management practices. Ethanol emission rates from loose silage were generally higher than previous estimates of total VOC emission rates from silage and mixed feed. For 15 cm deep loose samples, mean cumulative emission was as high as 170 g m^?2 (80% of initial ethanol mass) after 12 h of exposure to an air velocity of 5 m s^?1. Emission rates measured with an emission isolation flux chamber were lower than rates measured in a wind tunnel and in an open setting. Results show that the US EPA emission isolation flux chamber method is not appropriate for estimating VOC emission rates from silage in the field.     

Impacts on seafloor geology of drilling disturbance in shallow waters

This paper describes the effects of drilling disturbance on the seafloor of the upper continental slope of the Campos Basin, Brazil, as a result of the project Environmental Monitoring of Offshore Drilling for Petroleum Exploration – MAPEM. Field sampling was carried out surrounding wells, operated by the company PETROBRAS, to compare sediment properties of the seafloor, including grain-size distribution, total organic carbon, and clay mineral composition, prior to drilling with samples obtained 3 and 22 months after drilling. The sampling grid used had 74 stations, 68 of which were located along 7 radials from the well up to a distance of 500 m. The other 6 stations were used as reference, and were located 2,500 m from the well. The results show no significant sedimentological variation in the area affected by drilling activity. The observed sedimentological changes include a fining of grain size, increase in total organic carbon, an increase in gibbsite, illite, and smectite, and a decrease in kaolinite after drilling took place.     

The genetic mating system of a sea spider with male-biased sexual size dimorphism: evidence for paternity skew despite random mating success

Male-biased size dimorphism is usually expected to evolve in taxa with intense male–male competition for mates, and it is hence associated with high variances in male mating success. Most species of pycnogonid sea spiders exhibit female-biased size dimorphism, and are notable among arthropods for having exclusive male parental care of embryos. Relatively little, however, is known about their natural history, breeding ecology, and mating systems. Here we first show that Ammothella biunguiculata, a small intertidal sea spider, exhibits male-biased size dimorphism. Moreover, we combine genetic parentage analysis with quantitative measures of sexual selection to show that male body size does not appear to be under directional selection. Simulations of random mating revealed that mate acquisition in this species is largely driven by chance factors, although actual paternity success is likely non-randomly distributed. Finally, the opportunity for sexual selection (I _s), an indirect metric for the potential strength of sexual selection, in A. biunguiculata males was less than half of that estimated in a sea spider with female-biased size dimorphism, suggesting the direction of size dimorphism may not be a reliable predictor of the intensity of sexual selection in this group. We highlight the suitability of pycnogonids as model systems for addressing questions relating parental investment and sexual selection, as well as the current lack of basic information on their natural history and breeding ecology.