Evaluation of Cu-PPHs as active catalysts for the SCR process to control NOx emissions from heavy duty diesel vehicles

Copper based catalysts supported on mesoporous materials, which were in turn based on a surfactant expanded zirconium phosphate for the formation of silica galleries in the interlayer space, were prepared by the impregnation method. They were then characterised and tested in the selective catalytic reduction of NO with ammonia as active catalysts for the control of the NOx emissions from heavy duty vehicles. Copper catalysts displayed a high catalytic performance, even in the presence of 14% (v/v) of H2O and 100 ppm of SO2. They also displayed improved catalytic behaviour when compared to a CuZSM5 catalyst.     

Prioritisation of farm scale remediation efforts for reducing losses of nutrients and faecal indicator organisms to waterways: a case study of New Zealand dairy farming

The international competitiveness of the New Zealand (NZ) dairy industry is built on low cost clover-based systems and a favourable temperate climate that enables cows to graze pastures mostly all year round. Whilst this grazed pasture farming system is very efficient at producing milk, it has also been identified as a significant source of nutrients (N and P) and faecal bacteria which have contributed to water quality degradation in some rivers and lakes. In response to these concerns, a tool-box of mitigation measures that farmers can apply on farm to reduce environmental emissions has been developed. Here we report the potential reduction in nutrient losses and costs to farm businesses arising from the implementation of individual best management practices (BMPs) within this tool-box. Modelling analysis was carried out for a range of BMPs targeting pollutant source reduction on case-study dairy farms, located in four contrasting catchments. Due to the contrasting physical resources and management systems present in the four dairy catchments evaluated, the effectiveness and costs of BMPs varied. Farm managements that optimised soil Olsen P levels or used nitrification inhibitors were observed to result in win-win outcomes whereby nutrient losses were consistently reduced and farm profitability was increased in three of the four case study farming systems. Other BMPs generally reduced nutrient and faecal bacteria losses but at a small cost to the farm business. Our analysis indicates that there are a range of technological measures that can deliver substantial reductions in nutrient losses to waterways from dairy farms, whilst not increasing or even reducing other environmental impacts (e.g. greenhouse gas emissions and energy use). Their implementation will first require clearly defined environmental goals for the catchment/water body that is to be protected. Secondly, given that the major sources of water pollutants often differed between catchments, it is important that BMPs are matched to the physical resources and management systems of the existing farm businesses.     

Ground laser remote sensing measurements of a Saharan dust outbreak in Central Spain. Influence on PM10 concentrations in the lower and upper Spanish plateaus

This paper presents the hourly evolution of a severe Saharan dust outbreak, (SDO), affecting Central Spain over July 23-24, 2004 measured with a laser remote sensing device at a location close to the Guadarrama mountain range foothills and its impact on PM10 levels (particles with an aerodynamic diameter below 10 microm) recorded at four contrasting monitoring stations located in the upper and lower Spanish plateau, some 170km apart. During the period of study the Saharan dust layer, (SDL), presented significant hourly variability in height (3600-1500m), depth (1500-700m) and aerosol dust loading (extinction coefficient, EC, 0.22-1.28km(-1)). Overnight layering was generally observed whereas a well mixed layer prevailed in the afternoon. The (SDO) impact on the lower levels took place approximately 12h after the (SDL) was initially observed and triggered by a descending dust enriched, evidencing the important role of subsidence over the presence of dust in lower altitudes. During the event, PM10 levels at all the stations exceeded EU air quality daily mean standards, 50 microgm(-3), on 2-4days. The maximum values ranged from 185 to 245 microgm(-3) depending on the monitoring station. The impact on PM10 spread from 2days in the upper plateau to 3-4 in the lower plateau, in agreement with the geographical location of the monitoring stations with respect to the southwest origin of the intrusion. The impact was even more dramatic on PM10 hourly concentrations, leading to maximum hourly peaks ranging from 322 to 598 microgm(-3) again depending on the monitoring station. Correlations between EC vertical profiles and PM10 hourly concentrations at the monitoring stations showed the great influence of the (SDO) on surface concentrations. The best linear fits corresponded to the extinction coefficients in the lower altitudes (close to the lower range of the device 500-650m), EC2, yielding satisfactory correlation coefficients ranging from 0.68 to 0.71. The low variability of the slope of each individual linear fit, 19.2%, shows the similar impact of (SDO) on the PM10 hourly concentrations recorded in the area under study.     

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.     

Assessment of the pollution impact on biomarkers of effect of a freshwater fish

Changes in biomarkers of fish captured from stressed environments may represent a reliable tool in revealing sublethal effects of the pollutants found in aquatic ecosystems. The response patterns of selected biochemical and morphological variables biomarkers of effect were assessed in adult females of an indigenous teleost Cnesterodon decemmaculatus, caught at a polluted site (San Francisco) of the Reconquista river (Buenos Aires, Argentina). Combined field-caging experiments with controlled laboratory exposure to clean media were performed. The biochemical parameters measured were specific activities of gill (Na+ + K+)-ATPase, liver AlaAT and AspAT, and brain AChE; LSI and CF were also calculated. The changes in gill (Na+ + K+)-ATPase and liver AlaAT activities of fish captured in the field in most cases were reversible after transfer to clean media. The results were interpreted in association with the physicochemical profile of the water samples taken simultaneously with the capture of the fish. Results suggested the suitability of the test species used as tools in environmental monitoring programs of risk assessment.     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia Usneoides (L.) in an industrialized area in Rio de Janeiro state, south east Brazil--Part I: PCDD and PCDF

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic Bromeliad species as biomonitor and measuring total deposition rates on funnels covered with polyurethane foams. Samples were collected during 78 days in V.R. and 95 days in PNI in winter (dry season, June-August 2003) and during 114 days in both areas in summer (rainy season, December 2003-February 2004). The PCDD/PCDF deposition rates ranged from 0.10 to 1.9 pg WHO-TEQ/(m2 day) in winter and from 0.11 to 2.2 pg WHO-TEQ/(m2 day) in summer. Deposition rates found in V.R. in summer were four- to ninefold higher than those measured in PNI, while in winter deposition rates in both regions were in the same range. Deposition rates in V.R. in summer were about five fold lower than those measured in 1996. PCDD/PCDF levels in biomonitor samples were between 0.95 and 14.6 ng WHO-TEQ/kg d.m. in winter and between 2.2 and 5.2 ng WHO-TEQ/kg d.m. in summer. In winter, concentrations found in V.R. were up to 11 times higher than those found in PNI, while in summer the levels measured in both areas were comparable. The homologue and isomer profiles found in the deposition as well as in the biomonitor samples from V.R. indicate that steel production is the main source of contamination in the region, whereas in PNI, the long range transport of these pollutants is the predominant contamination pathway.     

Environmental assessment of water-courses of the Turvo Limpo River basin at the Minas Gerais State, Brazil

A study was performed to evaluate the environmental contamination in the Turvo Limpo River basin which receives effluent discharges from domestic (residential and commercial) activities. The watercourses examined were the São Bartolomeu Stream, Turvo Sujo River, and Turvo Limpo River, located in the Minas Gerais State, Brazil. Water samples were collected at the river-side and analyzed for evaluation of pollutant inputs. The pH, temperature, electrical conductivity, redox potential (Eh), dissolved oxygen (DO), total and settleable solids, visual color, hardness, chemical oxygen demand (COD), biochemical oxygen demand (BOD), chloride, total phosphate, total nitrogen, ammonia nitrogen, nitrate, total coliforms and E. coli, as well as the Cd, Pb, Cu, and Zn speciation were determined in the watercourses. The data obtained were compared with those of the Brazilian Environmental Standards and with data from non-contaminated areas. River water characteristics in some sites were far from the limit values established for superficial waters with satisfactory quality. For instance, the BOD values reached 411 mg L^?1 for a maximum limit of 10.0 mg L^?1, while the ammonia nitrogen concentration reached 28 mg L^?1 for a maximum limit of 13.3 mg L^?1. Some sites showed E. coli values above those of non-contaminated regions. Besides the effects of sewage discharges into the water-courses, agriculture activities and the use of the area for cattle husbandry influenced the quality of the river waters, for instance, the pH of a spring-water sample reached the value of 4.3. The São Bartolomeu Stream has been contributing to the deterioration of the water quality of the Turvo Sujo River, while the Turvo Limpo River has also been affected by anthropogenic discharges in the Turvo Sujo River. The speciation of Cd, Cu and Pb showed that these metals were mainly found in the particulate fraction (i. e., associated with the suspended material). Fifty five percent of the water samples showed labile Zn concentrations greater than that of the nonlabile Zn.