Assessment of decadal changes in sediment contamination in a large connecting channel (Detroit River,North America)

Concentrations of selected heavy metals (Cd, Cu, Hg, Pb, Zn) and organic contaminants (PCBs, PAHs) were investigated in samples from the Detroit River (Great Lakes, North America) in 1999 and 2008/09 collected using a stratified random sampling design. Getis–Ord geospatial analysis was used to further establish locations of areas demonstrating significantly high and low contaminant concentrations in the river. Based on the stratified random sampling design, a majority of the examined metals and organic contaminants demonstrated little or no trends with respect to regional sediment concentrations and river-wide mass balances over the investigated time interval. The Getis–Ord analysis revealed local scales of contaminated and clean areas which did not conform to the original strata used in the geostatistical sampling design. It is suggested that geospatial analyses such as Getis–Ord be used in the design of future sediment quality surveys to refine locations of strata that can simultaneously address sediment recovery over system-wide, regional and local spatial scales.     

Influence of sea-land breezes on the tempospatial distribution of atmospheric aerosols over coastal region

The influence of sea-land breezes (SLBs) on the spatial distribution and temporal variation of particulate matter (PM) in the atmosphere was investigated over coastal Taiwan. PM was simultaneously sampled at inland and offshore locations during three intensive sampling periods. The intensive PM sampling protocol was continuously conducted over a 48-hr period. During this time, PM2.5 and PM(2.5-10) (PM with aerodynamic diameters < 2.5 microm and between 2.5 and 10 microm, respectively) were simultaneously measured with dichotomous samplers at four sites (two inland and two offshore sites) and PM10 (PM with aerodynamic diameters < or =10 microm) was measured with beta-ray monitors at these same 4 sites and at 10 sites of the Taiwan Air Quality Monitoring Network. PM sampling on a mobile air quality monitoring boat was further conducted along the coastline to collect offshore PM using a beta-ray monitor and a dichotomous sampler. Data obtained from the inland sites (n=12) and offshore sites (n=2) were applied to plot the PM10 concentration contour using Surfer software. This study also used a three-dimensional meteorological model (Pennsylvania State University/National Center for Atmospheric Research Meteorological Model 5) and the Comprehensive Air Quality Model with Extensions to simulate surface wind fields and spatial distribution of PM10 over the coastal region during the intensive sampling periods. Spatial distribution of PM10 concentration was further used in investigating the influence of SLBs on the transport of PM10 over the coastal region. Field measurement and model simulation results showed that PM10 was transported back and forth across the coastline. In particular, a high PM10 concentration was observed at the inland sites during the day because of sea breezes, whereas a high PM10 concentration was detected offshore at night because of land breezes. This study revealed that the accumulation of PM in the near-ocean region because of SLBs influenced the tempospatial distribution of PM10 over the coastal region.     

Time-resolved measurements of aerosol elemental concentrations in indoor working environments

We have measured the elemental concentrations in aerosols with a 2-h time resolution in two different types of working environment: a chemistry laboratory dealing with the processing of advanced nanoparticulate materials and a medium-sized machine workshop. Non-stop 10-day and 12-day samplings were performed at each location in order to determine the concentration trends during the non-working/working and weekday/weekend periods. Supplementary measurements of PM10 aerosols with a 2-day sample collection time were performed with a standard Gent PM10 sampler to compare the elemental concentrations with the time-averaged concentrations detected by the 2D step-sampler. The concentrations were determined a posteriori by analyzing the x-ray spectra of aerosol samples emitted after 3-MeV proton bombardment. The PM10 samples collected in the chemistry laboratory were additionally inspected by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) to determine the chemical compositions of the individual particles. In the workshop, a total PM10 mass sampling was performed simultaneously with a minute resolution to compare the signal with typical outdoor PM10 concentration levels. A factor analysis of the time-resolved dataset points to six and eight factors in the chemistry laboratory and the machine workshop, respectively. These factors describe most of the data variance, and their composition in terms of different elements can be related to specific indoor activities and conditions. We were able to demonstrate that the elemental concentration sampling with hourly resolution is an excellent tool for studying the indoor air pollution. While sampling the total PM10 mass concentration with a minute resolution may lack the potential to identify the emission sources in a “noisy” environment, the time averaging on a day time scale is too coarse to cope with the working dynamics, even if elemental sensitivity is an option.     

Sources and distribution of polycyclic aromatic hydrocarbons in sediments from the Spanish northern continental shelf. Assessment of spatial and temporal trends

The distribution of polycyclic aromatic hydrocarbons was determined in surface sediments collected at 36 stations along the Spanish Northern continental shelf in March and September 2003, and February 2005. Concentrations of PAHs (Σ13 parent components) were in the range of 22-47528 μg/kg dw, the highest values corresponding to coastal urban-industrial hotspots and decreasing offshore. Sediment quality guidelines (SQGs) showed that concentrations of total PAHs were below the threshold effect level (TEC) in 27 stations (81%) and above in 7, two of which (Gijon and Bilbao) were above the probable effect concentration (PEC). The detailed study of diagnostic ratios suggested a rather uniform mixture of petrogenic and pyrolytic PAH sources along the continental shelf, with a slight decrease of the latter moving westwards and offshore. In order to assess the incidence of sediment sampling on the variability of the results, selected stations were also monitored in February and September 2004 and September 2005. The average field variance of the values obtained for each station was 31% that decreased to 23% when the values were normalized to TOC.     

Monitoring anthropogenic sewage pollution on mangrove creeks in southern Mozambique: a test of Palaemon concinnus Dana, 1852 (Palaemonidae) as a biological indicator

Tropical coastal ecosystems, such as mangroves, have a great ecological and socioeconomic importance for adjacent systems and local populations, but intensive environmental impact monitoring is still lacking, mainly in East Africa. This study evaluated the potential anthropogenic disturbance on Palaemon concinnus population structure and fitness. Palaemon concinnus populations from one peri-urban (domestic sewage impacted) and two pristine mangrove creeks were studied by sampling nearly 100 shrimps per location every 15 days for 12 months. The shrimps at the peri-urban location were larger, experienced longer reproductive periods, presented higher proportion of ovigerous females and better embryo quality when compared with shrimps inhabiting pristine locations. Physiological indices (RNA/DNA ratio) were similar between shrimps at pristine and peri-urban mangroves. However, a higher level of parasitation by a Bopyridae isopod, Pseudione elongata indicated some degree of stress on the host at the peri-urban mangrove, with potential effects on the host population dynamics.     

Small-scale spatial and temporal variance in the concentration of heavy metals in aquatic sediments: a review and some new concepts.

Uncertainty associated with data derived by the analyses of heavy metals in aquatic sediment is due to variance produced in the laboratory (precision), plus 'natural', small-scale spatial variance, (or field variance) at the sampling site. Precision is easily determined and is usually reported in contaminant studies, but field variance is poorly understood and seldom documented. It is important to have an understanding of the field variance because if small-scale spatial variance in the concentration of heavy metals is excessive, regional trends may be limited value. Similarly, if temporal change is large, the results of single synoptic surveys may be questionable and the ability to demonstrate anthropogenic contributions over time will be difficult. However, it is evident from the literature that the information needed to address problems of spatial and temporal variance in the field is beyond the resources of most researchers. Analytical precision of about 5% relative standard deviation (RSD) for heavy metal analysis is typical of a well-managed laboratory. Many studies of small-scale spatial variability made during the current investigation indicate that field variance is related to ambient energy and to the type of sedimentological environment. Total variance (analytical plus field variance) is approximately 10% RSD (mean for a suite of nine trace elements) for depositional parts of estuaries and the marine environment, but increases to about 20-35% RSD for the more dynamic parts of the estuarine environment and the fluvial system. Repeated sampling over periods of up to 7 years undertaken during the present study, indicate a similar order of magnitude for temporal variability in these sedimentological environments. A proposed scheme to provide information on field variance is to undertake small-scale spatial and temporal studies in discrete sedimentological environments in the study area after sediment sampling and characterisation has been completed. The comparatively large proportion of total variance associated with small-scale spatial and temporal variability in the field questions the often excessive cost and effort made in attempting minor reductions in analytical precision in contaminant investigations.     

Evaluation of the measurement uncertainty in automated long-term sampling of PCDD/PCDFs

Since the publication of the first version of European standard EN-1948 in 1996, long-term sampling equipment has been improved to a high standard for the sampling and analysis of polychlorodibenzo-p-dioxin (PCDD)/polychlorodibenzofuran (PCDF) emissions from industrial sources. The current automated PCDD/PCDF sampling systems enable to extend the measurement time from 6–8 h to 15–30 days in order to have data values better representative of the real pollutant emission of the plant in the long period. EN-1948:2006 is still the European technical reference standard for the determination of PCDD/PCDF from stationary source emissions. In this paper, a methodology to estimate the measurement uncertainty of long-term automated sampling is presented. The methodology has been tested on a set of high concentration sampling data resulting from a specific experience; it is proposed with the intent that it is to be applied on further similar studies and generalized. A comparison between short-term sampling data resulting from manual and automated parallel measurements has been considered also in order to verify the feasibility and usefulness of automated systems and to establish correlations between results of the two methods to use a manual method for calibration of automatic long-term one. The uncertainty components of the manual method are analyzed, following the requirements of EN-1948-3:2006, allowing to have a preliminary evaluation of the corresponding uncertainty components of the automated system. Then, a comparison between experimental data coming from parallel sampling campaigns carried out in short- and long-term sampling periods is realized. Long-term sampling is more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Automated sampling systems can assure very useful emission data both in short and long sampling periods. Despite this, due to the different application of the long-term sampling systems, the automated results could not be directly compared with manual results, not even in terms of measurement uncertainty. This investigation focuses on both uncertainty and repeatability of the automated sampling method. The standard 20988, developed by Internarional Organization of Standardization (ISO) can be used to estimate the measurement uncertainty. The results confirm that the uncertainties of manual and automated methods are comparable. At the same time, it is not appropriate to consider the manual method as a reference for the evaluation of the uncertainty of the automated sampling system, due to the high variability of both systems.     

Polycyclic aromatic hydrocarbons in ambient air in the Philippines derived from passive sampler with polyurethane foam disk

Passive samplers with polyurethane disks (PUF) were applied in the determination of the concentration of polycyclic aromatic hydrocarbons (PAHs) in ambient air in six residential areas in the Philippines during four simultaneous sampling periods. The uptake profiles of PAHs were determined at one site during one sampling period. Most of the PAHs that were detected in air at concentrations that were significantly higher than their analytical detection limits exhibited a linear uptake trend on the PUF disk. The linear uptake profiles of some high molecular weight (HMW) PAHs were not established and this is attributed to the low concentration of the compounds in air in the gaseous phase. The retention concentrations of phenanthrene-d-10 were determined after depuration in four sampling sites during two sampling periods. The sampling rate for phenanthrene-d-10 was calculated at the linear phase of the uptake using the k_A derived from depuration experiments and the relationship of k_A and sampling rate which was established in a previous passive sampling study. The average sampling rate obtained for phenanthrene d-10 (2.94±0.69 m³ d⁻¹) was applied for derivation of the concentrations of the PAHs in the field samples.The passive sampler with PUF disk and short integration time of 42–56 days is applicable for the derivation of the concentrations of PAHs in ambient air in the Philippines. The concentrations of the organic pollutants derived from the passive sampler showed variability for the six residential areas; reflecting the influence of possible sources of emission of the pollutants at the sites at the different sampling periods. The weather conditions, including the occurrence of a tropical cyclone, increased rainfall and high-relative humidity during the rainy season, had an influence on the concentrations of PAHs derived by the passive sampler.     

Evaluation of zoobenthic assemblages and recovery following petroleum spill in a coastal area of Río de la Plata estuarine system, South America

The objective of this work was to analyse zoobenthic assemblages in the coastal sector of the Río de La Plata, Argentina, after a petroleum spill. Sampling stations were located in representative sites of various landscapes. Structure, composition, physico-chemical parameters and seasonal changes were recorded in order to assess taxocenosis evolution during the period 1999–2003. Recovery signs were estimated by means of biotic indices and the presence of sensitive species. Tolerant species were dominant in heavily polluted sites, with low diversity and water quality values, according to the biotic indices used. In certain zones, sediment quality remains impoverished, with a visible oil film on the surface. However, during the last sampling, some points showed an increase in biotic indices, pointing to a slight improvement in environmental conditions.     

National status and trends mussel watch program: chlordane-related compounds in Gulf of Mexico oysters, 1986-1990

The National Oceanic and Atmospheric Administration's National Status and Trends (NS&T) Program has been monitoring the chemical contamination in bivalve tissues from the US coastal waters since 1986. alpha-Chlordane, trans-nonachlor, heptachlor and heptachlor epoxide, components of technical chlordane, are among the chlorinated pesticides measured. The geographical distribution of these chlordane compounds in oyster samples from the US Gulf of Mexico is well-established. For example, highest residue levels, predominantly alpha-chlordane and trans-nonachlor, were encountered in samples collected near highly populated areas in contrast with the concentrations measured in predominantly agricultural areas. Data collected during 5 years of bivalve sampling are used to evaluate temporal trends in residue concentrations at most NS&T sites. Minor decreases can be observed in the concentrations of alpha-chlordane and trans-nonachlor. Heptachlor and its epoxide concentrations, in contrast, have been increasing since 1987.     

Red-throated loons (Gavia stellata) breeding in Alaska,USA, are exposed to PCBs while on their Asian wintering grounds

Red-throated loons (Gavia stellata) breeding in Alaska declined 53% during 1977–1993. We compare concentrations of environmental contaminants in red-throated loons among four nesting areas in Alaska and discuss potential ramifications of exposure on reproductive success and population trends. Eggs from the four areas had similar total polychlorinated biphenyl (PCB) concentrations, but eggs from the Arctic coastal plain had different congener profiles and greater toxic equivalents (TEQs) than eggs from elsewhere. Satellite telemetry data indicate that red-throated loons from the Arctic coastal plain in northern Alaska winter in southeast Asia, while those breeding elsewhere in Alaska winter in North America. Different wintering areas may lead to differential PCB accumulation among red-throated loon populations. For eggs from the Arctic coastal plain, TEQs were great enough to postulate PCB-associated reproductive effects in piscivores. The correlation between migration patterns and PCB profiles suggests that red-throated loons breeding in northern Alaska are exposed to PCBs while on their Asian wintering grounds.     

Novel sampling methods for atmospheric semi-volatile organic compounds (SOCs) in a high altitude alpine environment

High- and low-volume active air samplers as well as bulk deposition samplers were developed to sample atmospheric SOCs under the adverse conditions of a mountain environment. Active sampling employed separate filters for different European source regions. Filters were switched depending on daily trajectory forecasts, whose accuracy was evaluated post hoc. The sampling continued on three alpine summits over five periods of four months. The prevailing trajectories varied stronger between sampling periods than between stations. The sampling equipment (active and bulk deposition) proved dependable for operation in a mountain environment, with idle times being mainly due to non-routine manipulations and connectivity.     

Statistical analysis of heavy metal data from municipal waste incineration residues

Heavy Metal data from a measurement program at a municipal incinerator in Vienna, Austria are analysed. The experimental design had a nested structure, and analysis of variance is used to break down the total variability into several components; (1) variability between mean hourly concentrations, (2) variability between mean sample concentrations within intervals of an hour and (3) variability due to “measurement” errors. Results of a pre-experiment show, that if grab samples are taken, within hour variation is dominant. The results of analysis of variance were used to calculate an optimal number of samples, which ensure a predetermined accuracy for the mean concentrations. In two main measuring periods with different incinerated waste types, slag and fly ash (ESP dust and boiler ash) data are produced and analysed. For both slag and fly ash, significant differences in measures of location and dispersion between the data sets of the main experiment are found. This proves, that differences in the chemical set up of waste can be detected via incineration residues.     

Detection and quantification of 2-methyltetrols in ambient aerosol in the southeastern United States

Filters collected from the Southeastern Aerosol Research and Characterization (SEARCH) air monitoring network were analyzed for the presence of 2-methyltetrols, namely 2-methylthreitol and 2-methylerythritol, two compounds that are products of the photooxidation of isoprene and have been detected in aerosol at a variety of sites around the globe. The 2-methytetrols were detected in ambient filter samples collected at the four SEARCH sites, Birmingham, AL, Centreville, AL, Pensacola, FL, and at Jefferson Street in Atlanta, GA, in late June 2004. Average atmospheric concentrations of 11.9 and 4.8 ng m⁻³ were measured for 2-methylerythritol and 2-methylthreitol, respectively, at the inland sampling sites, whereas average concentrations of 4.9 and 1.6 ng m⁻³ were measured at the coastal sampling location (Pensacola). On average, the aerosol loading from these two compounds accounts for approximately 0.42% and 0.21% of the organic mass collected on a given sampling day at the inland and coastal sites, respectively. The present data on these compounds, which are particulate-phase fingerprints of isoprene photooxidation, add to the growing body of ambient data on secondary organic aerosol from isoprene.     

Atmospheric mercury monitoring survey in Beijing,China

With the aid of one industrial, two urban, two suburban, and two rural sampling locations, diurnal patterns of total gaseous mercury (TGM) were monitored in January, February and September of 1998 in Beijing, China. Monitoring was conducted in six (two urban, two suburban, one rural and the industrial sites) of the seven sampling sites during January and February (winter) and in four (two urban, one rural, and the industrial sites) of the sampling locations during September (summer) of 1998. In the three suburban sampling stations, mean TGM concentrations during the winter sampling period were 8.6, 10.7, and 6.2 ng/m3, respectively. In the two urban sampling locations mean TGM concentrations during winter and summer sampling periods were 24.7, 8.3, 10, and 12.7 ng/m3, respectively. In the suburban-industrial and the two rural sampling locations, mean mercury concentrations ranged from 3.1-5.3 ng/m3 in winter to 4.1-7.7 ng/m3 in summer sampling periods. In the Tiananmen Square (urban), and Shijingshan (suburban) sampling locations the mean TGM concentrations during the summer sampling period were higher than winter concentrations, which may have been caused by evaporation of soil-bound mercury in warm periods. Continuous meteorological data were available at one of the suburban sites, which allowed the observation of mercury concentration variations associated with some weather parameters. It was found that there was a moderate negative correlation between the wind speed and the TGM concentration at this suburban sampling location. It was also found that during the sampling period at the same site, the quantity of TGM transported to or from the sampling site was mainly influenced by the duration and frequency of wind occurrence from certain directions.     

Estimating the spatial scale of herbicide and soil interactions by nested sampling, hierarchical analysis of variance and residual maximum likelihood

An unbalanced nested sampling design was used to investigate the spatial scale of soil and herbicide interactions at the field scale. A hierarchical analysis of variance based on residual maximum likelihood (REML) was used to analyse the data and provide a first estimate of the variogram. Soil samples were taken at 108 locations at a range of separating distances in a 9 ha field to explore small and medium scale spatial variation. Soil organic matter content, pH, particle size distribution, microbial biomass and the degradation and sorption of the herbicide, isoproturon, were determined for each soil sample. A large proportion of the spatial variation in isoproturon degradation and sorption occurred at sampling intervals less than 60 m, however, the sampling design did not resolve the variation present at scales greater than this. A sampling interval of 20-25 m should ensure that the main spatial structures are identified for isoproturon degradation rate and sorption without too great a loss of information in this field.     

Determination of Hg and diet identification in otter (Lontra longicaudis) feces

An analytical procedure for the determination of Hg in otter (Lontra longicaudis) feces was developed, to separate fish scales for the identification of the animal diet. Samples were washed with ultra-pure water and the suspension was sampled and transferred for digestion. The solubilization was performed with nitric-perchloric acid mixture, and detection carried out by the atomic fluorescence spectrometry (AFS). The quality of the analytical procedure was assessed by analyzing in-house standard solutions and certified reference materials. Total Hg concentrations were in the range of 7.6-156 ng g(-1) (July 2004), 25.6-277 ng g(-1) (January 2005) and 14.6-744 ng g(-1) (May 2005) that is approximately the same order of magnitude for all samples collected in two reservoirs at the Tiete River, Brazil. Although Hg concentrations varied with sampling periods and diet, high levels were correlated to the percentage of carnivorous fish scales present in the otter feces.     

A comparison of air quality indices for a port and harbour region in India

The present paper discusses and compares four different air quality indices, viz. arithmetic, multiplicative, unweighted arithmetic, and unweighted multiplicative, which were considered for characterising the coastal air quality at the Jawaharlal Nehru Port, Mumbai, India. Suspended particulate matter, oxides of nitrogen, and sulphur dioxide were used as the parameters of air quality indices. Value function graphs for above-mentioned variables were developed using Indian ambient air quality standards for different areas. Product moment correlation coefficients for various air quality indices were determined using the SPSS software package to evaluate correlation among various indices.