Toxicity and trace metal concentrations of sediments from Lake Maryut, Alexandria, Egypt.
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A new marine sediment reference material (NMIJ CRM 7301-a) for butyltins analysis was prepared and certified by the National Metrological Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). The original material of the sediment was collected at a bay near industrial activities in Japan. The sediment material was air-dried, sieved, homogenized, and packaged into 1,000 glass bottles (60 g each). Certification of NMIJ CRM 7301-a was carried out at NMIJ using two different types of species-specific isotope dilution mass spectrometry: isotope dilution-ethylation-gas chromatography/inductively coupled plasma mass spectrometry (GC/ICPMS) and isotope dilution-ethylation-gas chromatography/mass spectrometry (GC/MS). A mixture of (118)Sn-enriched monobutyltin, dibutyltin, and tributyltin was synthesized in our laboratory and was used as a spike for both techniques. Certified values are given for tributyltin (0.044+/-0.004 mg kg(-1) as Sn), dibutyltin (0.056+/-0.006 mg kg(-1) as Sn, and monobutyltin (0.058+/-0.013 mg kg(-1) as Sn), being at lower levels than currently available sediment CRMs for the analysis of organotins.
The accumulation of 14C-benzo(a)pyrene (BaP) sorbed to sediment was examined in fathead minnows (Pimephales promelas) to compare uptake from sediment with a high organic carbon (OC) content (7.7%), to that with a low OC content (2%). Ingestion of sediments was quantified by co-labeling the sediment with 141Cerium, which was not assimilated by the fish. Results of this study indicated that (1) significantly greater quantities of BaP were dissolved in water over low-OC sediment, compared to water over high-OC sediment, (2) fish disturbed the sediment and increased the concentration of BaP in centrifuged (particle-free) water, (3) fish ingested significantly more of the low-OC sediment than high-OC sediment, perhaps in response to the lower food quality of the low-OC sediment, and (4) uptake of BaP from sediment ingestion contributed <3% of the total flux of BaP into the fish. Primarily as a result of the greater concentration of BaP in water, fish from the low-OC exposures had significantly higher rates of BaP accumulation. However, after 48 h the body burdens in these fish declined by 50%, likely due to the induction of MFO enzymes in response to accumulation of BaP. A smaller effect was apparent in the fish from the high-OC exposures, consistent with the lower dose of BaP they experienced. These results illustrate the complex, and sometime counterintuitive, interactions that affect the uptake and bioaccumulation of sediment-associated contaminants.
Sediment and water samples collected from 32 locations in Ulsan Bay and adjacent inland areas were analyzed for polycyclic aromatic hydrocabons (PAHs), nonylphenol (NP), octylphenol (OP), bisphenol A (BPA), organochlorine (OC) pesticides (HCB, HCHs, CHLs, and DDTs), and polychlorinated biphenyls (PCBs) to characterize their spatial distribution and contamination status. PAHs were detected in nearly all sediment and water extracts from Ulsan Bay and its inland locations. The sedimentary PAH concentrations ranged from 17 to 3,100 ng/g on a dry weight basis (DW), which were predominated by two- and three-ring aromatic hydrocarbons in river and/or stream, and four- to six-ring compounds in Ulsan Bay sediment. Concentrations of PAHs in pore water samples were generally two or three orders magnitude less than those of corresponding sediment samples. Maximum concentrations of NP, OP, and BPA in sediments were 1,040, 120, and 54 ng/g DW, respectively. Concentrations of OP and BPA were, on average, 5- to 13-fold less than those of NP. PCB concentrations in sediment ranged from 1.4 to 77 ng/g DW, which were predominated by lower chlorinated congeners such as di- through pentachlorinated biphenyls. Among different OC pesticides analyzed, concentrations of DDTs were the greatest, ranging from 0.02 to 41.9 ng/g DW. NP concentrations were greater at inner locations proximal to municipal wastewater discharges into rivers and/or streams, whereas the concentrations of PCBs and PAHs were great near the sites of high industrial activities. Sediment-pore water partitioning coefficients correlated with those of reported Koc or Kow values for selected PAHs in Ulsan Bay, but these varied by an order of magnitude for stream and/or river sediments.
The use of an as-yet-undescribed euryhaline Corophium sp. amphipod as a sediment toxicity testing organism was assessed. The species was found to be ubiquitous in many tidal areas of the Hawkesbury River catchment. The salinity of habitat sites ranged from 0.1 to 24 ppt, sediment total organic carbon (TOC) ranged from 0.4% to 3.5%, and the fines content (< 63 micron particle size) of the sediment ranged from 4.3% to 47.6%. Monitored populations ranged from a density of 59 to 6622 individuals per m2, with freshwater sites with a sediment fines content greater than 20% having the highest population densities. The sensitivity of the Corophium sp. was assessed by using copper chloride and ammonium chloride as reference toxicants in a 96-h static water-only test and a 10-day static sediment test. The LC50 for copper in freshwater-only exposures was 80 to 86 microg/L, using adult animals collected from the field. In contrast, the LC50 for copper in freshwater sediment and the sediment pore water were 840 mg/kg (dry weight) and 99 microg/L, respectively. The LC50 for ammonia (total) in freshwater-only at pH 7 was 5.5 mg/L. In contrast, the LC50 for ammonia (total) in freshwater sediment and the sediment pore water were 110 mg/kg (dry weight) and 6 mg/L, respectively. Laboratory cultures of 5 per thousand to 15 per thousand salinity were optimal for supporting the release of juveniles. Juveniles collected from laboratory cultures had a LC50 for copper in 5 per thousand and 10 per thousand salinity of 9 microg/L and 28.5 microg/L, respectively, in water-only exposures. The juveniles would be suitable for use in the development of a chronic sediment toxicity test with growth as the endpoint.
Habitat equivalency analysis (HEA) was developed as a tool to scale mitigation or restoration when habitat is contaminated by hazardous substances or has been otherwise harmed by anthropogenic activities. Applying HEA involves balancing reductions in habitat quality against gains from restoration actions, and quantifying changes in habitat quality in terms of ecological services. We propose a framework for developing ecological service definitions and measures that incorporate knowledge about the impacts of chemical contaminants on biota. We describe a general model for integrating multiple lines of evidence about the toxicity of hazardous substances to allow mapping of toxicological inputs to ecological service losses. We provide an example of how this framework might be used in a HEA that quantifies ecological services provided by estuarine sediments contaminated with polycyclic aromatic hydrocarbons.
The different pools in the sediment from two bays with different scales of cyanobacterial bloom were studied to assess the trophic status. With large scale of cyanobacterial bloom in Haigeng bay the concentrations of different phosphorus fractions were higher than the corresponding concentrations in Macun bay, and especially WSP and AAP are the most evident, which indicates that there are more available and potential available phosphorus in Haigeng bay. The adsorption experiment also shows that the sediment in Haigeng bay is more saturated than that in Macun bay. Haigeng bay can be faced with the more serious ecological danger. Furthermore the death and deposit of a mass of algae can contribute to phosphorus released from sediment and help to the breakout of newborn cyanobacterial blooms.
Hyalella azteca (Crustacea: Amphipoda), water and sediments from 12 circum-neutral lakes between Sudbury and North Bay in Ontario, Canada were sampled in August 1998 and analyzed for 10 metals including Cu, Zn, Cd, Ni, Pb, Co, Mo, V, Ba and Ti. Statistical analyses showed that concentrations of the metals in H. azteca, water and sediment differed significantly (ANOVA, P<0.05) among lakes (except for Zn and Pb in H. azteca and Mo in water). There was a trend of declining metal concentration, especially for Cu, Ni and Co (in water, Hyalella and sediment), with distance from the smelters indicating the reduced impact of atmospheric pollution. Metal concentrations of lakes (water) in the Sudbury area were found to be lower compared to data from the 1970s and 1980s indicating an improvement in water quality. Metal concentrations in field-collected amphipods compared favorably with those measured in the laboratory in animals exposed to deep-water sediments, provided metal concentrations were not extremely low (e.g., Pb) and that water chemistry differences (e.g., pH) were taken into account for some metals (especially Cd). In general bioaccumulation of metals in H. azteca was predicted better from surface water than from sediment total metal.
Sorption and desorption behaviors of phenanthrene and naphthalene were studied with the whole sediment, humic acid (HA) and humin samples from downstream and upstream sites along the Kishon River, Israel. The 13C nuclear magnetic resonance spectra and the sorption coefficients suggest that sorption occurs to both aromatic and aliphatic moieties of the sedimentary organic matter and that rigid paraffinic domains probably contribute to the sorption non-linearity. The carbon-normalized Freundlich affinity values for the two sorbates were significantly higher for the whole sediment and humin samples from the downstream region of the river than for the upstream sediment samples. On the basis of the measured affinity values, the sorbents can be arranged in the following order: humin>HA>whole sediment. Phenanthrene exhibited the lowest desorption from the whole sediment samples compared with the other sorbents. For naphthalene, the desorption hysteresis obtained with the whole sediment and humin samples were similar: both exhibited a decrease in desorption with decreasing solute concentration. The higher sorption affinities observed for all the organic fractions from the downstream sediment are suggested to be related to the low levels of polar domains and humin content. It is concluded that in bulk sediment samples, the overall contribution of the HA fraction to short-term sorption is of high importance, but the sorption non-linearity is controlled mainly by the humin complexes. The low desorption potential recorded for the whole sediment samples could affect the natural attenuation of the sorbed hydrophobic organic compounds.
Bioassays are widely used to estimate ecological risks of contaminated sediments. We compared the results of three whole sediment bioassays, using the midge larva Chironomus riparius, the water louse Asellus aquaticus, and the mayfly nymph Ephoron virgo. We used sediments from sixteen locations in the Dutch Rhine-Meuse Delta that differed in level of contamination. Previously developed protocols for each bioassay were followed, which differed in sediment pretreatment, replication, and food availability. The Chironomus bioassay was conducted in situ, whereas the other two were conducted in the laboratory. The measured endpoints, survival and growth, were related to contaminant levels in the sediment and to food quantity in water and sediment. Only the response of A. aquaticus in the bioassay was correlated with sediment contamination. Food availability in overlying water was much more important for C. riparius and E. virgo, thereby masking potential sediment contaminant effects. We conclude that growth of A. aquaticus was depressed by sediment contamination, whereas growth of E. virgo and C. riparius was stimulated by seston food quantity. We discuss that the trophic state of the ecosystem largely affects the ecological risks of contaminated sediments.
This paper aimed at proposing rearing and testing protocols for Valvata piscinalis, a new potential species for sediment toxicity testing. Such tests were developed since this species reliably represents the bio/ecological characteristics of other gastropods. It may thus be representative of their sensitivity to chemicals. V. piscinalis was successfully cultured in our laboratory for six generations. Cultures provided a high productivity for a low working time and low costs. The tests conditions we proposed seemed to be relevant for the development of reliable tests with this species. Indeed, hatching probability of egg-capsules, as well as embryo, newborn and juvenile survival rates, were close to 100%. Moreover, growth rates and fecundity were significantly higher than in field and in other laboratory studies. Partial life-cycle tests on clean sediments were achieved for various feeding levels to determine survival, growth and reproduction patterns, ad libitum feeding level and life cycle parameters values. Ad libitum feeding levels for newborn, juveniles and adults were 0.1, 0.4 and 0.8 mg Tetramin/individual/working day. Growth tests with zinc-spiked sediments provided a no-effect concentration and a lowest effect concentration of respectively 200 and 624 mg zinc/kg dry sediment. Other growth tests on spiked sediments we ran at our laboratory with second, third and fourth instars larvae of Chironomus riparius pointed out that V. piscinalis was more sensible to zinc than the chironomid, which is a routine test species in ecotoxicology. According to these results, V. piscinalis is a promising candidate species for sediment toxicity testing.
To assess the ca. 20-year polychlorinated biphenyl (PCB) contamination trends in Lake Hartwell, SC, sediment cores from the Twelve Mile Creek arm were collected in July 2004 at two sites (G30 and G33) first sampled in the mid-1980s. Congener-specific PCB data as a function of depth from the sediment-water interface for the 2004 sediment samples were compared to data obtained from 1987 and 1998 samples taken from the same locations. Despite modest decreases in total PCB levels near the G30 sediment-water interface, historical increases in average degrees of chlorination may elevate the overall toxic risk at this site. Unlike G30, the more rapid recovery in the near-surface sediment of G33 suggests that the effectiveness of the U.S. EPA natural attenuation record of decision is site-specific and is unlikely to result in uniform surface sediment recovery throughout the most contaminated regions of Lake Hartwell.
A high performance liquid chromatography-electrospray (negative) ionization-tandem mass spectrometry (HPLC-ESI(-)-MS-MS) based method has been developed for simultaneous determination of bisphenol A (BPA), tetrachlorobisphenol A (TCBPA), and tetrabromobisphenol A (TBBPA), as well as lower brominated BPA analogues in sediment and sludge samples. Samples were extracted with MTBE, target compounds were partitioned by aqueous solution of sodium hydroxide. The solution was subsequently acidified, and the enrichment and desalting were performed via solid phase extraction (SPE). After cleanup the target compounds were determined by HPLC-ESI(-)-MS-MS. The method limits of quantification (MLOQs) from sediment and sludge for BPA, monobromo-bisphenol A (mono-BBPA), dibromo-bisphenol A (di-BBPA), tribromo-bisphenol A (tri-BBPA), TBBPA and TCBPA were 0.15, 0.02, 0.02, 0.04, 0.05, and 0.03 ng/g (dry weight), respectively. Mean recovery of the analytes from spiked samples ranged from 70 to 105%, and the relative standard deviation ranged from 4.9 to 13.1%. The method was successfully applied to sediment and sludge samples analysis.
A rapid method for the screening of polychlorinated biphenyls (PCBs) in sediment samples is described. Analytes are concentrated on a poly(dimethylsiloxane) (PDMS) solid-phase microextraction (SPME) fibre, separated using a narrow-bore gas chromatography column (10 m x 0.1mm I.D.) and determined with a micro-electron-capture detector (micro-ECD). The narrow-bore column showed a similar separation efficiency to a conventional capillary one (30 m x 0.32 mm I.D.) and allowed a 3 times reduction in the analysis time. Moreover, thermal desorption of SPME fibres in the narrow-bore column did not produce any degradation in the quality of separations when compared to the split injection mode. The use of an oxidative sample treatment was mandatory to remove sulphur interferences in the chromatograms and increase the yield of PCBs during SPME for short sampling times. Under optimised conditions, a fraction of sediment (0.1-0.5 g) was mixed with 5 ml of a 0.2M potassium permanganate solution and 0.5 ml of sulphuric acid 6M in a 22 ml closed vessel. Sample treatment and headspace SPME of PCBs were performed simultaneously for 10 min at 100 degrees C. Globally, the whole analytical procedure takes about 20 min and presents quantification limits between 0.5 and 1.3 ng/g. Accuracy was evaluated by analysing a reference sediment sample with certified concentrations of several PCBs.