Chemical techniques for assessing bioavailability of sediment-associated contaminants: SPME versus Tenax extraction

The traditional approach for predicting the risk of hydrophobic organic contaminants (HOCs) in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects to organisms. However, due to the multiple variables controlling bioavailability, this method has limitations. A matrix independent method of predicting bioavailability needs to be used in order to be universally applicable. Both chemical activity (freely dissolved chemical concentrations) measured by solid-phase microextraction (SPME) and bioaccessibility (rapidly desorbing fraction) estimated by Tenax extraction have been developed to predict bioavailability of sediment-associated HOCs. The objectives of this review are to summarize a number of studies using matrix-SPME or Tenax extraction to estimate bioavailability and/or toxicity of different classes of HOCs and evaluate the strengths and weakness of these two techniques. Although the two chemical techniques assess different components of the matrix, estimates obtained from both techniques have been correlated to organism body residues. The advantages of SPME fibers are their applicability for use in situ and their potential usage for a wide array of contaminants by selection of appropriate coatings. Single time-point Tenax extraction, however, is more time- and labor-effective. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants. This review also calls for additional research to evaluate the role of sequestrated contaminants and ingestion of sediment particles by organisms on HOC bioavailability. The use of performance reference compounds to reduce SPME sampling time and linking chemical based bioavailability estimates to toxicological endpoints are essential to expand the applications of these methods.     

Field uptake rates of hydrophobic organic contaminants by semipermeable membrane devices: environmental monitoring considerations

The uptake rates of selected hydrophobic organic contaminants (HOCs) by semipermeable membrane devices (SPMDs)--a polyethylene layflat containing the lipid triolein--were investigated under natural conditions. SPMDs were exposed in three sampling sites (industrial, urban, and agricultural areas) in the Tajo River (Toledo, Spain) for 5, 11 and 20 d. The organochlorine compounds 4,4'-DDT, 4,4'-DDE, alpha-HCH, gamma-HCH, pentachlorobenzene, hexachlorobenzene, and polychlorinated biphenyls (PCBs), and the 16 priority pollutant polycyclic aromatic hydrocarbons (PAHs) were detected in the SPMDs deployed in the three sampling sites. A linear uptake rate was found for DDTs and for 4-Cl- and 5-Cl-substituted PCB congeners in all sampling sites. Concentrations of HCHs (80.3 ng g(-1) SPMD for alpha-HCH and 109 ng g(-1) SPMD for gamma-HCH after 20 d of exposure) increased according to a linear uptake rate in the SPMDs deployed in the sampling site located in the agricultural area. Likewise, a marked increase of total PAH concentration (up to 300 ng g(-1) SPMD after 20 d of exposure) was solely found in the sampling site situated near a thermoelectric power station. Examination of individual PAHs revealed that PAHs with log K(OW) between 4.2 and 5.7 displayed a linear uptake rate over the 20 d of exposure. Water concentrations (ng L(-1)) of HCB (0.80-2.48), lindane (1.30-11.5), 4,4'-DDT (0.61-2.02), 4,4'-DDE (6.89-11.6) and total PAHs (12.0-26.7) estimated by a linear uptake kinetic model were found to be high in comparison with other polluted aquatic systems, and similar to concentrations in other Spanish rivers. Our results suggest that SPMD kinetic uptake studies in the natural environment are recommended for identifying point-pollution sources, and that shorter times of SPMD exposure (approximately 1 week) are desirable to minimize one of the main problems of field SPMD deployment, i.e., the biofouling, which negatively affects the estimation of the dissolved HOC concentrations.     

Comparative evaluation of a bioluminescent bacterial assay in terrestrial ecotoxicity testing

Despite the widespread and successful use of luminescence-based bioassays in water testing, their applications to soils and sediments is less proven. In part this is because such bioassays have mainly been carried out in an aqueous-based medium and, as such, favour contaminants that are readily water-soluble. In this study, aqueous solutions and soils contaminated with heavy metals (HM), polar organic contaminants and hydrophobic organic contaminants (HOCs) were tested using a range of luminescence-based bioassays (Vibrio fischeri, Escherichia coli HB101 pUCD607 and Pseudomonas fluorescens 10586r pUCD607). For the first two chemical groups, the assays were highly reproducible when optimised extraction procedures were employed but for HOCs the bioassay response was poor. Quantitative structure-activity relationships (QSARs) obtained from aqueous solutions had a linear response although correlation for the chemicals tested using bacterial bioassays was significantly less sensitive than that of sublethal tests for Tetrahymena pyriformis. Bacterial and Dendrobaena veneta bioassay responses to extracts from HM amended soils showed that a clear relationship between trophic levels could be obtained. There is no doubt that the wide range of bioluminescent-based bioassays offers complementary applications to traditional testing techniques but there is a significant need to justify and optimise the extraction protocol prior to application.     

Assessing organic contaminant fluxes from contaminated sediments following dam removal in an urbanized river

In this study, methods and approaches were developed and tested to assess changes in contaminant fluxes resulting from dam removal in a riverine system. Sediment traps and passive samplers were deployed to measure particulate and dissolved polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the water column prior to and following removal of a small, low-head dam in the Pawtuxet River, an urbanized river located in Cranston, RI, USA. During the study, concentrations of particulate and dissolved PAHs ranged from 21.5 to 103 μg/g and from 68 to 164 ng/L, respectively. Overall, temporal trends of PAHs showed no increases in either dissolved or particulate phases following removal of the dam. Dissolved concentrations of PCBs were very low, remaining below 1.72 ng/L at all sites. Particulate PCB concentrations across sites and time showed slightly greater variability, ranging from 80 to 469 ng/g, but with no indication that dam removal influenced any increases. Particulate PAHs and PCBs were sampled continuously at the site located below the dam and did not show sustained increases in concentration resulting from dam removal. The employment of passive sampling technology and sediment traps was highly effective in monitoring the concentrations and flux of contaminants moving through the river system. Variations in river flow had no effect on the concentration of contaminants in the dissolved or particulate phases, but did influence the flux rate of contaminants exiting the river. Overall, dam removal did not cause measurable sediment disturbance or increase the concentration or fluxes of dissolved or particulate PAHs and PCBs. This is due in large part to low volumes of impounded sediment residing above the dam and highly armored sediments in the river channel, which limited erosion. Results from this study will be used to improve methods and approaches that assess the short- and long-term impacts ecological restoration activities such as dam removal have on the release and transport of sediment-bound contaminants.     

Performance of semipermeable membrane devices for sampling of organic contaminants in groundwater

Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.     

Porous silica spheres as indoor air pollutant scavengers

Porous silica spheres were investigated for their effectiveness in removing typical indoor air pollutants, such as aromatic and carbonyl-containing volatile organic compounds (VOCs), and compared to the commercially available polymer styrene-divinylbenzene (XAD-4). The silica spheres and the XAD-4 resin were coated on denuder sampling devices and their adsorption efficiencies for VOCs evaluated using an indoor air simulation chamber. Real indoor sampling was also undertaken to evaluate the affinity of the silica adsorbents for a variety of indoor VOCs. The silica sphere adsorbents were found to have a high affinity for polar carbonyls and found to be more efficient than the XAD-4 resin at adsorbing carbonyls in an indoor environment.     

Concentrations of some heavy metals in water, suspended solids, and biota species from Maluan Bay, China and their environmental significance

Concentrations of heavy metals (Cu, Zn, Cd, and Pb) in surface water (including total recoverable, dissolved, suspended solids) and in aufwuchs encrusted on Moerella iridescens Benson from seven selected sites and two reference sites in Maluan Bay were investigated in order to understand current metal contamination due to industrialization and urbanization in Xiamen, China. The muscle tissues of the study species (Penceus penicillatus, Scylla serrata Forskal, Harengula zunasi Bleeker, Tillapia nilotica) from a trawling area within Maluan Bay were also analyzed in order to evaluate its safety as seafood. Based on the obtained data, metal concentrations in surface water were compared with Marine Seawater Quality Standards of China and the US EPA acute and chronic criteria, which showed that Maluan Bay may be subjected to different levels of contamination by the metals. Metal concentrations under study in the edible parts (muscle) of the investigated biota species were within the safety permissible levels for human consumption. Through Pearson??s correlation analysis, the relationships between metal concentrations in surface water and in M. iridescens were evaluated. Copper concentrations in M. iridescens were more strongly positively correlated with particulate copper in suspended solids and total recoverable copper in water rather than with dissolved copper at the sampling sites. The data suggested that copper-rich suspended solids contributed substantially to copper accumulation by M. iridescens and played a critical role in the pathway of copper into the food chain. The conclusions of this investigation are likely to be applicable to other relevant scenarios.     

Fluorescence spectroscopic characterization of dissolved organic matter fractions in soils in soil aquifer treatment

This work investigated the effect of soil aquifer treatment (SAT) operation on the fluorescence characteristics of dissolved organic matter (DOM) fractions in soils through laboratory-scale soil columns with a 2-year operation. The resin adsorption technique (with XAD-8 and XAD-4 resins) was employed to characterize the dissolved organic matter in soils into five fractions, i.e., hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N), and hydrophilic fraction (HPI). The synchronous fluorescence spectra revealed the presence of soluble microbial byproduct- and humic acid-like components and polycyclic aromatic compounds in DOM in soils, and SAT operation resulted in the enrichment of these fluorescent materials in all DOM fractions in the surface soil (0–12.5 cm). More importantly, the quantitative method of fluorescence regional integration was used in the analysis of excitation–emission matrix (EEM) spectra of DOM fractions in soils. The cumulative EEM volume (Φ _{T, n} ) results showed that SAT operation led to the enrichment of more fluorescent components in HPO-A and TPI-A, as well as the dominance of less fluorescent components in HPO-N, TPI-N, and HPI in the bottom soil (75–150 cm). Total Φ _{T, n} values, which were calculated as $ {\Phi_{{T,n}}} \times {\mathrm{DOC}} $ , suggested an accumulation of fluorescent organic matter in the upper 75 cm of soil as a consequence of SAT operation. The distribution of volumetric fluorescence among five regions (i.e., P _{i, n} ) results revealed that SAT caused the increased content of humic-like fluorophores as well as the decreased content of protein-like fluorophores in both HPO-A and TPI-A in soils.     

The role of hydrodynamics, matrix and sampling duration in passive sampling of polar compounds with Empore SDB-RPS disks

There is an increasing need to monitor concentrations of polar organic contaminants in the aquatic environment. Integrative passive samplers can be used to assess time weighted average aqueous concentrations, provided calibration data are available and sampling rates are known. The sampling rate depends on environmental factors, such as temperature and water flow rate. Here we introduce an apparatus to investigate the sampling properties of passive samplers using river-like flow conditions and ambient environmental matrices: river water and treated sewage effluent. As a model sampler we selected Empore SDB-RPS disks in a Chemcatcher housing. The disks were exposed for 1 to 8 days at flow rates between 0.03 and 0.4 m s(-1). Samples were analysed using a bioassay for estrogenic activity and by LC-MS-MS target analysis of the pharmaceuticals sulfamethoxazole, carbamazepine and clarithromycin. In order to assess sampling rates of SDB disks, we also measured aqueous concentrations of the pharmaceuticals. Sampling rates increased with increasing flow rate and this relationship was not affected by the environmental matrix. However, SDB disks were only sampling in the integrative mode at low flow rates <0.1 m s(-1) and/or for short sampling times. The duration of linear uptake was particularly short for sulfamethoxazole (1 day) and longer for clarithromycin (5 days). At 0.03 m s(-1) and 12-14 degrees C, the sampling rate of SDB disks was 0.09 L day(-1) for clarithromycin, 0.14 L day(-1) for sulfamethoxazole and 0.25 L day(-1) for carbamazepine. The results show that under controlled conditions, SDB disks can be effectively used as passive sampling devices.     

Post-remediation evaluation of a LNAPL site using electrical resistivity imaging

Present understanding of the earth's subsurface is most often derived from samples at discrete points (wells) and interpolations or models that interpret the space between these points. Electrical resistivity imaging techniques have produced an improved capability to map contaminants (especially NAPLs--NonAqueous Phase Liquids) away from traditional wells using actual field data. Electrical resistivity image data, confirmed by drilling, have demonstrated that LNAPL (Light NAPL--less dense than water, such as gasoline) contaminants exist outside of a delineated and remediated area in Golden, Oklahoma. The data also demonstrate that LNAPL exists between monitoring and remediation wells which indicate low contaminant levels when sampled. Additionally, the electrical images provided the drilling location with the highest concentration of hydrocarbon ever found on the site, even after two phases of remediation work had been performed, although the sampling protocols varied. The results indicate that current methods of post-remediation site characterization are inadequate for complete site characterization.     

Investigating the impacts of treated effluent discharge on coastal water health (Visakhapatnam,SW coast of Bay of Bengal,India)

The present study investigated the impacts of treated effluent discharge on physicochemical and biological properties of coastal waters from three pharmaceuticals situated along the coast of Visakhapatnam (SW Bay of Bengal). Seawater samples were collected (during the months of December 2013, March 2014 and April 2014) from different sampling locations (Chippada (CHP), Tikkavanipalem (TKP) and Nakkapalli (NKP)) at 0- and 30-m depths within 2-km radius (0.5 km = inner, 1 km = middle and 2 km?=?outer sampling circles) from the marine outfall points. Physicochemical and biological parameters, which differed significantly within the stations, were likely to be influenced by strong seasonality rather than local discharge. Dissolved oxygen variability was tightly coupled with both physical and biological processes. Phytoplankton cell density and total chlorophyll (TChla) concentrations were significantly correlated with dissolved inorganic nutrient concentrations. CHP (December) represented a diatom bloom condition where the highest concentrations of diatom cells, total chlorophyll (TChla), dissolved oxygen coupled with lower zooplankton abundance and low nutrient levels were noticed. The centric diatom, Chaetoceros sp. (>?50%) dominated the phytoplankton community. TKP (March) represented a post-diatom bloom phase with the dominance of Pseudo-nitzschia seriata; zooplankton abundance and nutrient concentrations were minimum. Conversely, NKP (April) represented a warm well-stratified heterotrophic period with maximum zooplankton and minimum phytoplankton density. Dinoflagellate abundance increased at this station. Relatively higher water temperature, salinity, inorganic nutrients coupled with very low concentrations of dissolved oxygen, TChla and pH were observed at this station. Copepods dominated the zooplankton communities in all stations and showed their highest abundance in the innermost sampling circles. Treated effluent discharge did not seem to have any significant impact at these discharge points.     

Inorganic and organic contaminants in Alaskan shorebird eggs

Many shorebird populations throughout North America are thought to be declining, with potential causes attributed to habitat loss and fragmentation, reduced prey availability, increased predation, human disturbance, and increased exposure to environmental pollutants. Shorebirds may be particularly vulnerable to contaminant exposure throughout their life cycle, as they forage primarily on invertebrates in wetlands, where many contaminants accumulate disproportionately in the sediments. Therefore, it is important to document and monitor shorebird populations thought to be at risk and assess the role that environmental contaminants may have on population declines. To investigate potential threats and provide baseline data on shorebird contaminant levels in Alaskan shorebirds, contaminant concentrations were evaluated in shorebird eggs from 16 species residing in seven geographic distinct regions of Alaska. Similar to previous studies, low levels of most inorganic and organic contaminants were found, although concentrations of several inorganic and organic contaminants were higher than those of previous studies. For example, elevated strontium levels were observed in several species, especially black oystercatcher (Haematopus bachmani) sampled in Prince William Sound, Alaska. Additionally, contaminant concentrations varied among species, with significantly higher concentrations of inorganic contaminants found in eggs of pectoral sandpiper (Calidris melanotos), semipalmated sandpiper (Calidris pusilla), black oystercatcher, and bar-tailed godwit (Limosa lapponica). Similarly, significantly higher concentrations of some organic contaminants were found in the eggs of American golden plover (Pluvialis dominica), black-bellied plover (Pluvialis squatarola), pacific golden plover (Pluvialis fulva), bar-tailed godwit, and semipalmated sandpiper. Despite these elevated levels, current concentrations of contaminants in shorebird eggs suggest that breeding environments are relatively free of most contaminants and that contaminant concentrations are below levels (except potentially strontium) that would likely affect the survival of individuals and consequently regulate the species at the population level.     

Passive sampling: partition coefficients for a silicone rubber reference phase

Silicone rubber sheeting can be used as a passive sampling device for hydrophobic organic contaminants in the environment to determine the available concentrations in water and sediments. Reliable sampler-water partition coefficients are required to determine the sampling rates and the dissolved contaminant concentrations in water and in sediment pore water. Log partition coefficients (logK(sr,w)) for silicone rubber-water have been estimated for 32 polycyclic aromatic hydrocarbons (PAHs), 2 deuterated PAH analogues and 32 chlorobiphenyls (CBs) using the cosolvent method, with methanol as cosolvent. Strong linear relationships were found with literature values for the corresponding log octanol-water partition coefficients (logK(ow)) for both CBs and PAHs, confirming that partitioning into the silicone rubber is strongly determined by the hydrophobicity of the compounds, which suggests logK(ow) is a good predictor of logK(sr,w) and that absorption is the main mechanism for accumulation of analytes into the silicone rubber polymer.     

An assessment of contamination of the Fusaro Lagoon (Campania Province,southern Italy) by trace metals

The Fusaro Lagoon is a shallow lagoon, located in SW Italy, largely influenced in the last decades by several anthropic impacts. The study examined the pollution status of the lagoon, during year 2011–2012 at nine sampling stations with the aim to find out proper measurements of water lagoon restoration. Concentrations of heavy metals (HMs) (aluminium [Al], barium [Ba], cadmium [Cd], copper [Cu], iron [Fe], manganese [Mn], vanadium [V] and zinc [Zn]) were examined in water, sediments and specimens of the ascidian Ciona intestinalis sp. A. Low levels of dissolved oxygen concentration were detected at many stations, with mean values of 5.2–6.4 mg L^?1. The redox potential of surface waters was also low, ?2.7 to 50.7 mV. Sediments possessed high organic matter content, 17.7–29.4 %. In sediments, the mean Zn level, 251.4 mg kg^?1, was about sixfold higher than that recorded in year 2000 (38.5 mg kg^?1) and considerably higher than that recorded in 2007 (191 mg kg^?1). The mean levels of Cd were outstandingly high, with a mean value of 70.5 mg kg^?1, about 30- and 50-fold higher than those determined in 2000 and 2007, respectively. Cadmium (Cd), Cu and nickel (Ni) appeared in excess with respect to most current guidelines, reaching significant pollution levels. C. intestinalis sp. A was detected only at few stations, with metals accumulated preferentially in the body in respect to the tunic, from 1.2 times for Zn (178 mg kg^?1) to 4.0 times for V (304 mg kg^?1). Data suggests the necessity of an immediate action of eco-compatible interventions for environmental restoration.     

Trace metal levels in Prochilodus lineatus collected from the La Plata River, Argentina

Most of the industrial, urban and sewage discharges are released into the La Plata River, Argentina without any previous treatment. However, few works have investigated the extent of metal contamination. The aim of this study was to assess the levels of cadmium, copper, lead and zinc in liver and gills of adults Prochilodus lineatus collected from three sampling stations along the coast of the La Plata River: Berazategui, Berisso and Atalaya (from north to south). Samplings were performed during 2002 and 2004. Berazategui and Berisso were located nearby the main ducts that discharge the urban and domestic waste disposal from the cities of Buenos Aires and La Plata, respectively. The third station, Atalaya, was free of sewage discharges. Levels of cadmium and copper in liver were always higher than those found in gills. Instead, for lead and zinc, high levels were observed either in liver or gills, depending on the sampling station and the sampling period. In both tissues, the concentrations of metals did not differ significantly between male and female fish. In liver samples, the concentrations of cadmium, copper and zinc tended to increase from north to south. Instead, the levels of lead followed an opposite pattern. No clear tendencies were observed in gill samples. The data may be useful as reference levels of metal contaminants in P. lineatus, the most important fish species in the La Plata River system.     

Determination of 7-ethoxyresorufin-o-deethylase (EROD) induction in leaping mullet (Liza saliens) from the highly contaminated Aliaga Bay, Turkey

Pollution of the aquatic environment is a global concern owing to the devastating effects of contaminants whose levels are growing at an alarming rate, and it has become a major threat for marine organisms, as well as to humans as consumers. This study has been carried out on leaping mullet obtained from Aliaga Bay, which is located on the west coast of the Aegean Sea near Izmir and hosts the world’s fifth largest shipyard, plus a broad range of industrial activities, including an oil refinery and a paper factory. The waste from these industries, combined with municipal sewer discharges, is the main cause of pollution in this region. There is no national documentation or research on the determination of pollution resulting from the industrial activities in this area. In the present study, the degree of induction of CYP4501A-associated 7-ethoxyresorufin O-deethylase (EROD) activity and immunochemical detection of CYP1A1 in the liver of leaping mullet (Lisa saliens) were used as biomarkers for the assessment of polycyclic aromatic hydrocarbon (PAH)-type organic pollutants in Aliaga Bay. Mullet caught from different locations of the bay had approximately 52 times more EROD activity than the feral fish sampled from a clean reference site near Foca, Izmir. The results of this study indicate that Aliaga Bay is highly contaminated with PAH-type organic pollutants.     

Sampling design for long-term regional trends in marine rocky intertidal communities

Probability-based designs reduce bias and allow inference of results to the pool of sites from which they were chosen. We developed and tested probability-based designs for monitoring marine rocky intertidal assemblages at Glacier Bay National Park and Preserve (GLBA), Alaska. A multilevel design was used that varied in scale and inference. The levels included aerial surveys, extensive sampling of 25 sites, and more intensive sampling of 6 sites. Aerial surveys of a subset of intertidal habitat indicated that the original target habitat of bedrock-dominated sites with slope ≤30° was rare. This unexpected finding illustrated one value of probability-based surveys and led to a shift in the target habitat type to include steeper, more mixed rocky habitat. Subsequently, we evaluated the statistical power of different sampling methods and sampling strategies to detect changes in the abundances of the predominant sessile intertidal taxa: barnacles Balanomorpha, the mussel Mytilus trossulus, and the rockweed Fucus distichus subsp. evanescens. There was greatest power to detect trends in Mytilus and lesser power for barnacles and Fucus. Because of its greater power, the extensive, coarse-grained sampling scheme was adopted in subsequent years over the intensive, fine-grained scheme. The sampling attributes that had the largest effects on power included sampling of “vertical” line transects (vs. horizontal line transects or quadrats) and increasing the number of sites. We also evaluated the power of several management-set parameters. Given equal sampling effort, sampling more sites fewer times had greater power. The information gained through intertidal monitoring is likely to be useful in assessing changes due to climate, including ocean acidification; invasive species; trampling effects; and oil spills.     

Determining storm sampling requirements for improving precision of annual load estimates of nutrients from a small forested watershed

This study sought to determine the lowest number of storm events required for adequate estimation of annual nutrient loads from a forested watershed using the regression equation between cumulative load (∑L) and cumulative stream discharge (∑Q). Hydrological surveys were conducted for 4 years, and stream water was sampled sequentially at 15-60-min intervals during 24 h in 20 events, as well as weekly in a small forested watershed. The bootstrap sampling technique was used to determine the regression (∑L-∑Q) equations of dissolved nitrogen (DN) and phosphorus (DP), particulate nitrogen (PN) and phosphorus (PP), dissolved inorganic nitrogen (DIN), and suspended solid (SS) for each dataset of ∑L and ∑Q. For dissolved nutrients (DN, DP, DIN), the coefficient of variance (CV) in 100 replicates of 4-year average annual load estimates was below 20% with datasets composed of five storm events. For particulate nutrients (PN, PP, SS), the CV exceeded 20%, even with datasets composed of more than ten storm events. The differences in the number of storm events required for precise load estimates between dissolved and particulate nutrients were attributed to the goodness of fit of the ∑L-∑Q equations. Bootstrap simulation based on flow-stratified sampling resulted in fewer storm events than the simulation based on random sampling and showed that only three storm events were required to give a CV below 20% for dissolved nutrients. These results indicate that a sampling design considering discharge levels reduces the frequency of laborious chemical analyses of water samples required throughout the year.     

Trophic dynamics of U, Ni, Hg and other contaminants of potential concern on the Department of Energy’s Savannah River Site

The Department of Energy’s Savannah River Site is a former nuclear weapon material production and current research facility located in South Carolina, USA. Wastewater discharges from a fuel and nuclear reactor target manufacturing facility released depleted and natural U, as well as other metals into the Tims Branch-Steed Pond water system. We investigated the current dynamics of this system for the purposes of environmental monitoring and assessment by examining metal concentrations, bioavailability, and trophic transfer of contaminants in seven ponds. Biofilm, detritus, and Anuran and Anisopteran larvae were collected and analyzed for stable isotopes (δ ¹⁵N, δ ¹³C) and contaminants of potential concern (COPC) with a focus on Ni, U, and Hg, to examine metal mobility. Highest levels of Ni and U were found in biofilms U (147 and 332 mg kg^?1 DW, respectively), while highest Hg levels were found in tadpoles (1.1 mg kg^?1 DW). We found intraspecific biomagnification of COPCs as expressed through stable isotope analysis. Biofilms were the best indicators for contamination and Anuran larvae with the digestive tract removed were the best indicators of the specific bioavailability of the focal metals. Monitoring data showed that baseline δ ¹⁵N values differed between ponds, but within a pond, values were stable throughout tadpole Gosner stage, strengthening the case to use this species for monitoring purposes. It is likely that there still is risk to ecosystem integrity as COPC metals are being assimilated into lower trophic organisms and even low levels of this mixture has shown to produce deleterious effects to some wildlife species.     

Assessment of bioavailable fraction of POPS in surface water bodies in Johannesburg City,South Africa,using passive samplers: an initial assessment

In this study, the semipermeable membrane device (SPMD) passive samplers were used to determine freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in selected water bodies situated in and around Johannesburg City, South Africa. The devices were deployed for 14 days at each sampling site in spring and summer of 2011. Time weighted average (TWA) concentrations of the water-borne contaminants were calculated from the amounts of analytes accumulated in the passive samplers. In the area of interest, concentrations of analytes in water ranged from 33.5 to 126.8 ng l^?1 for PAHs, from 20.9 to 120.9 pg l^?1 for PCBs and from 0.2 to 36.9 ng l^?1 for OCPs. Chlorinated pesticides were mainly composed of hexachlorocyclohexanes (HCHs) (0.15–36.9 ng l^?1) and dichlorodiphenyltrichloromethane (DDT) with its metabolites (0.03–0.55 ng l^?1). By applying diagnostic ratios of certain PAHs, identification of possible sources of the contaminants in the various sampling sites was performed. These ratios were generally inclined towards pyrogenic sources of pollution by PAHs in all study sites except in the Centurion River (CR), Centurion Lake (CL) and Airport River (AUP) that indicated petrogenic origins. This study highlights further need to map up the temporal and spatial variations of these POPs using passive samplers.