A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

The analysis of monitoring data with the aid of time-series analysis

Methods derived from time-series analysis are proposed for processing monitoring data. The necessity for the use of these methods is demonstrated. In a case study time-series analysis was applied to assess the impact of the closure of the Grevelingen estuary (S. W. Netherlands) in 1971 on a local wintering population of Oystercatchers (Haematopus ostralegus) in the adjacent Oosterschelde estuary.Communication No. 328 of the Delta Institute for Hydrobiological Research.     

Seasonal variations of monocarbonyl and dicarbonyl in urban and sub-urban sites of Xi’an,China

Seventeen airborne carbonyls including monocarbonyls and dicarbonyls were determined in urban and sub-urban sites of Xi’an, China in three seasons in 2010. In winter, acetone was the most abundant carbonyl in the urban site due to usage of organic solvents in constructions and laboratories and its slower atmospheric removal mechanisms by photolysis and reaction with hydroxyl radical than those of formaldehyde and acetaldehyde. In the sub-urban site, acetaldehyde was the most abundant carbonyl, followed by formaldehyde and acetone. During summer, however, formaldehyde was the most dominant carbonyl in both sites. The photooxidations of a wide range of volatile organic compounds (VOCs) yielded much more formaldehyde than other carbonyls under high solar radiation and temperature. In the urban site, the average concentrations of dicarbonyls (i.e., glyoxal and methyglyoxal) in spring and summer were higher than that in winter. Transformation of aromatic VOCs emitted from fuel evaporation leads to the formation of 1,2-dicarbonyls. A reverse trend was observed in sub-urban sites, as explained by the relatively low abundances and accumulations of VOC precursors in the rural atmosphere during warm seasons. Moreover, cumulative cancer risk based on measured outdoor carbonyls (formaldehyde and acetaldehyde) in Xi’an Jiaotong University and Heihe was estimated (8.82?×?10^?5 and 4.96?×?10^?5, respectively). This study provides a clear map on the abundances of carbonyls and their source interpretation in the largest and the most economic city in Northwestern China.     

Serial batch leaching procedure for characterization of coal fly ash

Although many leaching methods have been used for various purposes by research groups, industries, and regulators, there is still a need for a simple but comprehensive approach to leaching coal utilization by-products and other granular materials in order to estimate potential release of heavy metals when these materials are exposed to natural fluids. A serial batch characterization method has been developed at the National Energy Technology Laboratory that can be completed in 2–3 days to serve as a screening tool. The procedure provides an estimate of cumulative metals release under varying pH conditions, and leaching the sample at increasing liquid/solid ratios can indicate the rate at which this process will occur. This method was applied to eight fly ashes, adapted to the acidic or alkaline nature of the ash. The leachates were analyzed for 30 elements. The test was run in quadruplicate, and the relative standard deviation (RSD) was used as a measure of method reproducibility. RSD values are between 0.02 and 0.70, with the majority of the RSD values less than 0.3. The serial batch leaching procedure was developed as a simple, relatively quick, yet comprehensive method of estimating the risk of heavy metal release from fly ash when it is exposed to natural fluids, such as acid rain or groundwater. Tests on a random selection of coal fly ashes have shown it to be a reasonably precise method for estimating the availability and long-term release of cations from fly ash.     

Monochlorobenzene Marine Risk Assessment with Special Reference to the Osparcom Region: North Sea

This risk assessment on monochlorobenzene was carried out for the marine environment, following methodology given in the EU risk assessment Regulation (1488/94) and Guidance Document of the EU New and Existing Substances Regulation (TGD, 1996). Data from analytical monitoring programmes in large rivers and estuaries in the North Sea area were collected and evaluated for effects and environmental concentrations. Risk is indicated by the ratio of predicted environmental concentration (PEC) to predicted no-effect concentration (PNEC) for the marine aquatic environment. In total, 27 data for fish, 24 data for invertebrates and 13 data for algae were evaluated. Acute and chronic toxicity studies were taken into account and appropriate assessment factors used to define a final PNEC value of 32 micro/l. Recent monitoring data indicate that monochlorobenzene levels in surface waters are below determination limits of 0.1, 0.2, 0.5 microg/l used in monitoring programs. Assuming that half of the lowest determination (0.1 microg/l) is typical, a PEC of 0.05 microg/l was derived. A worst case of 0.5 microg/l is assumed. PEC/PNEC ratios give safety factors of 60 to over 500, taking no account of dilution in the sea. Monochlorobenzene is not a 'toxic, persistent and liable to bioaccumulate' substance sensu the Oslo and Paris Conventions for the Prevention of Marine Pollution (OSPAR-DYNAMEC) criteria. Environmental fate and effects data indicate that current use of monochlorobenzene poses no unacceptable risk to the aquatic environment.     

Integrating Remote Sensing Approach with Pollution Monitoring Tools for Aquatic Ecosystem Risk Assessment and Managment: A Case Study of Lake Victoria(UGANDA)

Aquatic ecosystems around the world, lake, estuaries and coastal areas are increasingly impacted by anthropogenic pollutants through different sources such as agricultural, industrial and urban discharges, atmospheric deposition and terrestrial drainage. Lake Victoria is the second largest lake in the world and the largest tropical lake. Bordered by Tanzania, Uganda, and Kenya, it provides a livelihood for millions of Africans in the region. However, the lake is under threat from eutrophication, a huge decline in the number of native fish species caused by several factors including loss of biodiversity, over fishing and pollution has been recently documented. Increasing usage of pesticides and insecticides in the adjacent agricultural areas as well as mercury contamination from processing of gold ore on the southern shores are currently considered among the most emergent phenomena of chemical contamination in the lake. By the application of globally consistent and comprehensive geospatial data-sets based on remote sensing integrated with information on heavy metals accumulation and insecticides exposure in native and alien fish populations, the present study aims at assessing the environmental risk associated to the contamination of the Lake Victoria water body on fish health, land cover distribution, biodiversity and the agricultural area surrounding the lake. By the elaboration of Landsat 7 TM data of November 2002 and Landsat 7 TM 1986 we have calculated the agriculture area which borders the Lake Victoria bay, which is an upland plain. This process has greatly enhanced nutrient loading to the soil, which is subsequently transported to the lake by rain or as dry fall. All the data has been insert in the Geographical information System (ARCGIS) to be upgraded and consulted. Heavy metals in fish fillets showed concentrations rather low except for mercury being higher than others as already described in previous investigations. In the same tissue, cholinesterases activity (ChE) as an indicator of insecticides exposure showed significant differences among fish species in both activity and sensitivity of selected inhibitor insecticides. This integrated approach aims at identifying and quantifying selected aquatic environmental issues which integrated with monitoring techniques such as contaminant concentrations and biological responses to insecticides exposure in fish populations will provide a scientific basis for aquatic zones management and assist in policy formulations at the national and international levels.     

Evidence supporting the importance of terrestrial carbon in a large-river food web

Algal carbon has been increasingly recognized as the primary carbon source supporting large-river food webs; however, many of the studies that support this contention have focused on lotic main channels during low-flow periods. The flow variability and habitat-heterogeneity characteristic of these systems has the potential to significantly influence food web structure and must be integrated into models of large-river webs. We used stable-isotope analysis and IsoSource software to model terrestrial and algal sources of organic carbon supporting consumer taxa in the main channel and oxbow lakes of the Brazos River, Texas, USA, during a period of frequent hydrologic connectivity between these habitat types. Standardized sampling was conducted monthly to collect production sources and consumer species used in isotopic analysis. Predictability of hydrologic connections between habitat types was based on the previous 30 years of flow data. IsoSource mixing models identified terrestrial C3 macrophytes (riparian origin) as the primary carbon source supporting virtually all consumers in the main channel and most consumers in oxbow lakes. Small-bodied consumers (<100 mm) in oxbow lakes assimilated large fractions of algal carbon whereas this pattern was not apparent in the main channel. Estimates of detritivore trophic positions based on delta15N values indicated that terrestrial material was likely assimilated via invertebrates rather than directly from detritus. High flows in the river channel influenced algal standing stock, and differences in the importance of terrestrial and algal production sources among consumers in channel vs. oxbow habitats were associated with patterns of flooding. The importance of terrestrial material contradicts the findings of recent studies of large-river food webs that have emphasized the importance of algal carbon and indicates that there can be significant spatial, temporal, and taxonomic variation in carbon sources supporting consumers in large rivers.     

Optimizing dispersal corridors for the Cape Proteaceae using network flow

We introduce a new way of measuring and optimizing connectivity in conservation landscapes through time, accounting for both the biological needs of multiple species and the social and financial constraint of minimizing land area requiring additional protection. Our method is based on the concept of network flow; we demonstrate its use by optimizing protected areas in the Western Cape of South Africa to facilitate autogenic species shifts in geographic range under climate change for a family of endemic plants, the Cape Proteaceae. In 2005, P. Williams and colleagues introduced a novel framework for this protected area design task. To ensure population viability, they assumed each species should have a range size of at least 100 km2 of predicted suitable conditions contained in protected areas at all times between 2000 and 2050. The goal was to design multiple dispersal corridors for each species, connecting suitable conditions between time periods, subject to each species' limited dispersal ability, and minimizing the total area requiring additional protection. We show that both minimum range size and limited dispersal abilities can be naturally modeled using the concept of network flow. This allows us to apply well-established tools from operations research and computer science for solving network flow problems. Using the same data and this novel modeling approach, we reduce the area requiring additional protection by a third compared to previous methods, from 4593 km2 to 3062 km , while still achieving the same conservation planning goals. We prove that this is the best solution mathematically possible: the given planning goals cannot be achieved with a smaller area, given our modeling assumptions and data. Our method allows for flexibility and refinement of the underlying climate-change, species-habitat-suitability, and dispersal models. In particular, we propose an alternate formalization of a minimum range size moving through time and use network flow to achieve the revised goals, again with the smallest possible newly protected area (2850 km2). We show how to relate total dispersal distance to probability of successful dispersal, and compute a trade-off curve between this quantity and the total amount of extra land that must be protected.