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.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

Effects of Roadway Crossings on Leaf Litter Processing and Invertebrate Assemblages in Small Streams

The effects of the Maine Turnpike (Interstate 95) on leaf litter processing were examined in five first- and second-order coastal plain streams in southern Maine, U.S.A. Invertebrate assemblages and red maple leaf softening and loss rates were compared at 53 stations arrayed upstream and downstream of the turnpike. Litter softening rate was not affected by the roadway. Litter loss rate was significantly faster at downstream stations (-0.0024 degree-day(-1)) than at upstream stations or at stations nearest the roadway, which were not different from each other (-0.0022 degree-day(-1)). Litter softening and loss rates were more strongly related to physical and chemical habitat variables than to shredder assemblage characteristics. Significant among-stream differences were observed in most community structural metrics and in biomass of important shredder taxa, but effects of the roadway were rarely consistent among streams. This is attributed in part to habitat variation, which was greater among streams than within streams. This study suggests that while the presence of the Maine Turnpike may influence stream water quality and habitat structure, the relatively subtle effects of roadway runoff and associated habitat modifications on stream ecosystem processes are masked by within- and among-stream variability in litter processing and leaf pack invertebrate assemblage structure.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

High frequency monitoring of the coastal marine environment using the MAREL buoy

The MAREL Iroise data buoy provides physico-chemical measurements acquired in surface marine water in continuous and autonomous mode. The water is pumped 1.5 m from below the surface through a sampling pipe and flows through the measuring cell located in the floating structure. Technological innovations implemented inside the measuring cell atop the buoy allow a continuous cleaning of the sensor, while injection of chloride ions into the circuit prevents biological fouling. Specific sensors for temperature, salinity, oxygen and fluorescence investigated in this paper have been evaluated to guarantee measurement precision over a 3 month period. A bi-directional link under Internet TCP-IP protocols is used for data, alarms and remote-control transmissions with the land-based data centre. Herein, we present a 29 month record for 4 parameters measured using a MAREL buoy moored in a coastal environment (Iroise Sea, Brest, France). The accuracy of the data provided by the buoy is assessed by comparison with measurements of sea water weekly sampled at the same site as part of SOMLIT (Service d'Observation du Milieu LIToral), the French network for monitoring of the coastal environment. Some particular events (impact of intensive fresh water discharges, dynamics of a fast phytoplankton bloom) are also presented, demonstrating the worth of monitoring a highly variable environment with a high frequency continuous reliable system.     

A pilot project to detect and forecast harmful algal blooms in the northern Gulf of Mexico

More timely access to data and information on the initiation, evolution and effects of harmful algal blooms can reduce adverse impacts on valued natural resources and human health. To achieve this in the northern Gulf of Mexico, a pilot project was initiated to develop a user-driven, end-to-end (measurements to applications) observing system. A key strategy of the project is to coordinate existing state, federal and academic programs at an unprecedented level of collaboration and partnership. Resource managers charged with protection of public health and aquatic resources require immediate notice of algal events and a forecast of when, where and what adverse effects will likely occur. Further, managers require integrated analyses and interpretations, rather than raw data, to make effective decisions. Consequently, a functional observing system must collect and transform diverse measurements into usable forecasts. Data needed to support development of forecasts will include such properties as sea surface temperature, winds, currents and waves; precipitation and freshwater flows with related discharges of sediment and nutrients; salinity, dissolved oxygen, and chlorophyll concentrations (in vivo fluorescence); and remotely-sensed spatial images of sea surface chlorophyll concentrations. These data will be provided via a mixture of discrete and autonomous in situ sensing with near real-time data telemetry, and remote sensing from space (SeaWiFS), aircraft (hyperspectral imagery) or land (high-frequency radar). With calibration across these platforms, the project will ultimately provide a 4-dimensional visualization of harmful algae events in a time frame suitable to resource managers.     

Using improved neural network model to analyze RSP,NOx and NO2 levels in urban air in Mong Kok,Hong Kong

As the health impact of air pollutants existing in ambient addresses much attention in recent years, forecasting of airpollutant parameters becomes an important and popular topic inenvironmental science. Airborne pollution is a serious, and willbe a major problem in Hong Kong within the next few years. InHong Kong, Respirable Suspended Particulate (RSP) and NitrogenOxides NO_x and NO₂ are major air pollutants due to thedominant diesel fuel usage by public transportation and heavyvehicles. Hence, the investigation and prediction of the influence and the tendency of these pollutants are ofsignificance to public and the city image. The multi-layerperceptron (MLP) neural network is regarded as a reliable andcost-effective method to achieve such tasks. The works presentedhere involve developing an improved neural network model, whichcombines the principal component analysis (PCA) technique and theradial basis function (RBF) network, and forecasting thepollutant levels and tendencies based in the recorded data. Inthe study, the PCA is firstly used to reduce and orthogonalizethe original input variables (data), these treated variables arethen used as new input vectors in RBF neural network modelestablished for forecasting the pollutant tendencies. Comparingwith the general neural network models, the proposed modelpossesses simpler network architecture, faster training speed,and more satisfactory predicting performance. This improvedmodel is evaluated by using hourly time series of RSP, NO_x and NO₂ concentrations collected at Mong Kok Roadside Gaseous Monitory Station in Hong Kong during the year 2000. By comparing the predicted RSP, NO_x and NO₂ concentrationswith the actual data of these pollutants recorded at the monitorystation, the effectiveness of the proposed model has been proven.Therefore, in authors' opinion, the model presented in the paper is a potential tool in forecasting air quality parameters and hasadvantages over the traditional neural network methods.     

Concentrations and profiles of polychlorinated biphenyls, -dibenzo-p-dioxins and -dibenzofurans in livers of mink from South Carolina and Louisiana,U.S.A

In South Carolina, U.S.A., mink have been reintroduced from two apparently healthy populations to areas where populations haveexisted in the past but have been extirpated. High mortality wasobserved during transport of mink from the source populations. Inorder to elucidate the potential effects of dioxin-like compoundson the survival and reproduction of mink, concentrations of totalpolychlorinated biphenyls (PCBs), p,p-DDE, dioxin-likePCBs, polychlorinated dibenzo-p-dioxins (PCDDs), anddibenzofurans (PCDFs) were measured in livers of mink collectedfrom the source populations in South Carolina and Louisiana. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxinequivalents (TEQs) for the South Carolina and Louisiana mink were21 and 14 pg g^-1, wet wt., respectively. PCB and TEQ concentrations were close to the threshold values that can, under laboratory conditions, elicit toxic effects in ranchmink. Therefore, any additional exposures of these populations toTEQs might adversely affect their populations.     

Sharing the geo-Referenced Results of Climate Change Impact Research

The Prairie Adaptation Research Collaborative (PARC) has implemented an Internet Map Server (IMS) at the PARC web site (www.parc.ca) to 1) disseminate the geo-referenced results of PARC sponsored research on climate change impacts and adaptation, and 2) address data, information and knowledge management within the PARC network of researchers and partners. PARC facilitates interdisciplinary research on adaptation to the impacts of climate change in the Canadian Prairie Provinces. The web site is intended as a platform for sharing information and encouraging discussion of climate change impacts and adaptation. The IMS enables scientists and stakeholders to apply simple climate change scenarios to geo-referenced biophysical and social data, and dynamically create maps that display the geographic distribution of potential impacts of climate change. With a limited capacity for spatial analysis, most geo-processing and the climate impact modeling is done offline within a GIS environment. The IMS will serve the output from climate impact models, such that the model results can be customized by the web site user and be most readily applied to the planning and analysis of adaptation strategies.     

Metal Pollution Assessment of Sediment and Water in the River Hindon, India

The metal pollution in water and sediment of the River Hindon in western Uttar Pradesh (India) was assessed for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn. The metal concentrations in water showed wide temporal variation compared with bed sediment because of variability in water discharge and variations in suspended solid loadings. Metal concentrations in bed sediments provided a better evaluation of the degree and the extent of contamination in the aquatic environment, Santagarh and Atali being the most polluted sites of the river. The ratio of heavy metals to conservative elements (Fe, Al, etc.) may reveal the geochemical imbalances due to the elevated metal concentrations normally attributed to anthropogenic sources. Metal/Al ratios for the bed sediments of the river Hindon were used to determine the relative mobility and general trend of relative mobility occurred Fe > Mn > Zn > Cr > Ni > Pb > Cu > Cd.