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[Contents and distribution characteristics of heavy metals in water and sediment of intertidalite].

ICP-MS analytical technology was used to analyze the concentration of 13 heavy metals in surface water, pore water in sediment, suspended particulate matter, and sediment of intertidalite of Tianjin. Results show that both total amount and single concentration of heavy metals vary greatly in different media, the biggest and smallest values differ by 4 or 7 magnitudes. While the variation coefficients of the contents of total metals or single metal in the same medium are less than 0.3 and 0.5 respectively except for the pore water. The average concentration of total dissolved heavy metals is 41.2 microg x L(-1), while total contents of heavy metals in original water, pore water, sediment and suspended particles are 62.7 microg x L(-1), 112.7 microg x L(-1), 262.3 mg x L(-1) and 345.0 mg x L(-1) respectively, they are similar to inland natural river but higher then those of ocean. The composition of heavy metals in different media varied greatly, metals prone to dissolve such as Mo account for more than 20% in water, but metals uneasy to dissolve mainly exist in sediment and suspended particles and absorbed by particles. Typical heavy metals, such as Zn, Cu, Pb and Cr, account for 40% - 50% in water and 50% - 80% in other media. The similarity in distribution mode of heavy metals in intertidalite and terrestrial soil suggest that they are originated from terrestrial soil that is contiguity to the sea. Notable correlativity can be seen between concentrations of all heavy metals except for Mo in sediment, which can explain the similarity of their environmental behavior, but only wake correlation between the content of organic carbon and concentrations of heavy metals in suspended particulates and sediment.

China↗

Using mathematical models to assess sediment stability.

The application of mathematical models to a sediment stability study is presented, with an emphasis on using models as a component of an effort to develop, refine, and potentially validate a conceptual site model (CSM) for sediment transport at a study site. The utility of mathematical models is discussed, in which the modeling framework consists of linked hydrodynamic, sediment transport, and contaminant fate and transport models. Benefits and drawbacks of empirically based mechanistic models are presented. An approach for integrating modeling analyses into the development, refinement and validation of a CSM is provided. This approach focuses on a phased study that combines modeling and data-based analyses to test hypotheses related to the CSM and sediment stability. Uncertainty in modeling results is a primary concern in sediment stability studies, and issues related to model uncertainty are discussed. Finally, communication of modeling results to stakeholders is addressed.

Environmental Pollutants↗

Tephrostratigraphy and the Acheulian to middle stone age transition in the Kapthurin Formation, Kenya.

Sites containing Acheulian, Sangoan, Fauresmith, and Middle Stone Age artefacts occur within and below the Bedded Tuff, a widespread volcaniclastic member of the Kapthurin Formation, Kenya. The Bedded Tuff eruptive complex consists of up to twelve tephra beds, intercalated sediments, and paleosols. Two pumiceous units, high in the Bedded Tuff sequence, have been dated by(40)Ar/(39)Ar, one to 235+/-2 ka (Deino & McBrearty, 2002, Journal of Human Evolution, 42, 185-210, cf. Tallon, 1978, Geological Background to Fossil Man, pp. 361-373, Scottish Academic Press), the other to 284+/-12 ka (Deino & McBrearty, 2001), the latter now providing a minimum age estimate for all underlying archaeological sites. Bedded Tuff outcrops are correlated through field stratigraphic and electron microprobe geochemical analyses of individual beds. Bedded Tuff units show increasingly evolved composition through the stratigraphic succession, indicating that the beds are the product of intermittent eruption of a single differentiating magma system, and the chemical signatures of these beds permit the chronological ordering of archaeological sites. Our results indicate that the transition to Middle Stone Age technology occurred prior to 285 ka in this region of East Africa. The interstratification of sites containing Acheulian, Sangoan, Fauresmith, and Middle Stone Age artefacts suggests that these technologies were contemporary in a single depositional basin over the duration of the transition.

Animals↗

Toxicity of weathered coal tar for shortnose sturgeon (Acipenser brevirostrum) embryos and larvae.

Weathered coal tar collected from the Connecticut River near Holyoke, Massachusetts, was toxic to shortnose sturgeon embryos and larvae in whole sediment flow-through and elutriate static-renewal laboratory exposures. Sterile laboratory sand and clean Connecticut River sand, collected upstream from the coal tar deposits, produced no significant difference in toxicity to sturgeon embryos-larvae, while coal tar-contaminated sediment produced over 95% embryo-larval mortality. Hydrocarbon transfer and subsequent toxicity appeared to be via direct contact of the embryos with contaminated sediment, rather than via exposure to soluble hydrocarbons. This conclusion was supported by exposure of embryos and larvae to elutriates (e.g., water soluble extract) of coal-tar sediments, that resulted in embryo and larval mortality at low molecular weight PAH concentrations-0.47 mg/L, higher than would occur naturally. No decrease in petroleum hydrocarbon concentration was observed in sediments exposed to flowing water for 14 d, supporting the contention that soluble hydrocarbons were not responsible for the observed toxicity in whole sediment exposures under the conditions employed in this study.

Animals↗

Certification of butyltins and phenyltins in marine sediment certified reference material by species-specific isotope-dilution mass spectrometric analysis using synthesized 118Sn-enriched organotin compounds.

A new marine sediment certified reference material, NMIJ CRM 7306-a, for butyltin and phenyltin analysis has been prepared and certified by the National Metrological Institute of Japan at the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Candidate sediment material was collected at a bay near industrial activity in Japan. After air-drying, sieving, and mixing the material was sterilized with gamma-ray irradiation. The material was re-mixed and packaged into 250 glass bottles (15 g each) and these were stored in a freezer at -30 degrees C. Certification was performed by use of three different types of species-specific isotope-dilution mass spectrometry (SSID-MS)-SSID-GC-ICP-MS, SSID-GC-MS, and SSID-LC-ICP-MS, with 118Sn-enriched organotin compounds synthesized from 118Sn-enriched metal used as a spike. The 118Sn-enriched mono-butyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were synthesized as a mixture whereas the 118Sn-enriched di-phenyltin (DPhT) and triphenyltin (TPhT) were synthesized individually. Four different extraction methods, mechanical shaking, ultrasonic, microwave-assisted, and pressurized liquid extraction, were adopted to avoid possible analytical bias caused by non-quantitative extraction and degradation or inter-conversion of analytes in sample preparations. Tropolone was used as chelating agent in all the extraction methods. Certified values are given for TBT 44+/-3 microg kg(-1) as Sn, DBT 51 +/- 2 microg kg(-1) as Sn, MBT 67 +/- 3 microg kg(-1) as Sn, TPhT 6.9 +/- 1.2 microg kg(-1) as Sn, and DPhT 3.4 +/- 1.2 microg kg(-1) as Sn. These levels are lower than in other sediment CRMs currently available for analysis of organotin compounds.

Chemistry Techniques, Analytical↗

The effects of sieving and spatial variability of estuarine sediment toxicity samples on sediment chemistry.

In 1998, we conducted a field-validation study of the chronic 28-day whole-sediment toxicity test with Leptocheirus plumulosus in Baltimore Harbor, MD, an area where this amphipod is indigenous. This study included an evaluation of the effect of sieving on sediment chemical concentrations and the use of field replicates, or separate grabs from the same site, which provided an estimation of within-site chemical and toxicologic variability. Six stations in Baltimore Harbor, MD, were included in this evaluation. Chemical analysis of two separate unsieved field replicates from the six sites indicated that, overall, the chemical concentrations of replicates within each site were similar, especially for metals. Organic contaminants particularly total PCBs, had the highest variability between replicates. Chemical variability did not appear to be related to differences in organic carbon content or grain size or to variability in toxicologic end points. Results supported the use of composite samples in sediment toxicity tests. In addition, in most cases, sieving had little effect on sediment chemistry. For the metals and trace elements, only selenium showed a substantial change after sieving, with some samples increasing after sieving and others decreasing. Concentrations of acid-volatile sulfide (AVS) increased 194.6% at one station after sieving, although in most other cases, AVS and simultaneously extracted metals remained relatively unchanged. As expected, concentrations of organics generally decreased after sieving, but in the majority of cases this decrease was small (i.e., coefficient of variation < or = 25%). Total benzene hexachloride and total chlordanes had the greatest changes, whereas polychlorinated biphenyl concentrations decreased at only two stations after sieving. Concentrations of polyaromatic hydrocarbons showed little change after sieving. These changes in sediment chemistry due to sieving must be viewed in the larger context of the potentially confounding effects that indigenous organisms may have on the interpretation of test results from whole-sediment toxicity tests.

Amphipoda↗

The relevance of rooted vascular plants as indicators of estuarine sediment quality.

Toxicity assessments and numerical quality assessment guidelines for estuarine sediments are rarely based on information for aquatic plants. The effect of this lack of information on contaminated sediment toxicity evaluations is largely unknown. For this reason, the toxicities of whole sediments collected from 15 sites in three urbanized Florida bayou-estuaries were determined for the benthic invertebrates Mysidopsis bahia and Ampelisca abdita and the plants Scirpus robustus Pursh (saltmarsh bulrush) and Spartina alterniflora Loisel (saltmarsh cordgrass). The results of the bioassays, conducted for 7 to 28 days, were compared for interspecific differences and to effects-based, sediment quality assessment guidelines. A variety of inorganic and organic analytes were detected in the estuarine sediments, and concentrations of as many as 7 analytes exceeded the sediment guidelines at the 15 sampling locations. Toxicity occurred at 2 of the 15 sampling stations based on invertebrate survival. Twelve of the 15 sediments had either a significant stimulatory or inhibitory effect on early seedling growth relative to a reference sediment (p < 0.05). The phytoresponse was specific to the location, test species, and plant tissue. There was no consistent trend between the sensitivities of the plants and invertebrates exposed to the sediments collected from the same sites. Of the 12 sediments that significantly affected seedling growth, 10 were not acutely toxic to the invertebrates. Consequently, the plant test species provided information that would have been missing if only animal test species were used. For this reason, the phytotoxicity database needs to be expanded for contaminated sediments to further evaluate interspecific sensitivities and to provide perspective on the environmental relevancy of proposed sediment quality criteria and effects-based assessment guidelines for which this information is usually missing. However, additional test method development and field validation are needed to support this effort, which includes the identification of sensitive plant test species, response parameters, and the chemical and physical sediment factors that influence plant growth.

Animals↗

Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes.

Patterns of isotopic fractionation in biogeochemical processes are reviewed and it is suggested that isotopic fractionations will be small when substrates are large. If so, isotopic compositions of biomarkers will reflect those of their biosynthetic precursors. This prediction is tested by consideration of results of analyses of geoporphyrins and geolipids from the Greenhorn Formation (Cretaceous, Western Interior Seaway of North America) and the Messel Shale (Eocene, lacustrine, southern Germany). It is shown (i) that isotopic compositions of porphyrins that are related to a common source, but which have been altered structurally, cluster tightly and (ii) that isotopic differences between geolipids and porphyrins related to a common source are equal to those observed in modern biosynthetic products. Both of these observations are consistent with preservation of biologically controlled isotopic compositions during diagenesis. Isotopic compositions of individual compounds can thus be interpreted in terms of biogeochemical processes in ancient depositional environments. In the Cretaceous samples, isotopic compositions of n-alkanes are covariant with those of total organic carbon, while delta values for pristane and phytane are covariant with those of porphyrins. In this unit representing an open marine environment, the preserved acyclic polyisoprenoids apparently derive mainly from primary material, while the extractable, n-alkanes derive mainly from lower levels of the food chain. In the Messel Shale, isotopic compositions of individual biomarkers range from -20.9 to -73.4% vs PDB. Isotopic compositions of specific compounds can be interpreted in terms of origin from methylotrophic, chemautotrophic, and chemolithotrophic microorganisms as well as from primary producers that lived in the water column and sediments of this ancient lake.

Alkanes↗

Determination of Np-237 by radiochemical neutron activation analysis combined with extraction chromatography.

A procedure for determination of 237Np, 238Pu, 239,240Pu and 241Pu in environmental samples is described. Neptunium-237 is determined using radiochemical neutron activation analysis with pre- and post-irradiation chemistry based on solvent extraction and extraction chromatography. 238Pu, 239,240Pu is determined using alpha spectrometry and 241Pu by liquid scintillation spectrometry. The vertical profiles of 237Np, 238Pu, 239,240Pu in bottom sediments from the Black Sea are presented.

Chromatography↗

Concentrations of heavy metal and radioactivity in surface water and sediment of Hazar Lake (Elaziğ, Turkey).

Concentration of heavy metals and natural gross radioactivity were measured in the surface water and sediment of Hazar Lake (Elaziğ, Turkey). Eight sampling sites were pre-defined in different locations of the lake. A preliminary study on heavy metals (Zn, Fe, Mn, Ni, Cu, Cr, Co and Pb), major elements (Na, K, Ca, Mg) concentrations and natural radioactivity related to 226Ra, gross-alpha and gross-beta radiations in the surface water and deep sediments were determined. The obtained results showed that, in general, the heavy metals (Zn, Fe, Mn, Ni, Cu and Pb) and major elements (Na, K, Ca, Mg) concentrations in water did not exceed WHO (World Health Organization, 1999), EC (Europe Community, 1998), EPA (Environment Protection Agency, 2002) and TSE-266 (Turkish Standard, 1997) guidelines. Generally, heavy metals and major elements concentration of the sediments were found decrease in sequence of Fe>Mg>Ca>Mn>Zn>Ni>Cr>Cu>Co>Pb. The results of this study indicated that a general absence of serious pollution in the Hazar Lake. The results obtained from the radioactivity determination indicate that the surface water radioactivity concentration of 226Ra, gross-alpha and gross-beta were ranging from 0.52+/-0.02 to 2.02+/-0.06 Bq/l and from 0.65+/-0.03 to 2.52+/-0.07 Bq/l and from 0.01+/-0.01 to 0.14+/-0.01 Bq/l, respectively. Deep sediment radioactivity concentrations of 226Ra is ranging from 0.07+/-0.03 to 0.32+/-0.07 Bq/g.

Environmental Monitoring↗

Testing sediment biological effects with the freshwater amphipod Hyalella azteca: the gap between laboratory and nature.

The freshwater amphipod, Hyalella azteca, is widely used in laboratory sediment toxicity and bioaccumulation tests. However, its responses in the laboratory are probably very different from those in the field. A review of the literature indicates that in its natural habitat this species complex is primarily epibenthic, derives little nutrition from the sediments, and responds primarily to contaminants in the overlying water column (including water and food), not sediment or porewater. In laboratory sediment toxicity tests H. azteca is deprived of natural food sources such as algal communities on or above the sediments, and is subjected to constant light without any cover except that afforded by burial into the sediments. Under these constraining laboratory conditions, H. azteca has been reported to respond to sediment or porewater contamination. In nature, contamination of overlying water from sediment is less likely than in the laboratory because of the large, generally non-static sink of natural surface water. H. azteca does not appear to be the most appropriate test species for direct assessments of the bioavailability and toxicity of sediment contaminants, though it is probably appropriate for testing the toxicity of surface waters. Toxic and non-toxic responses will be highly conservative, though the latter are probably the most persuasive given the exposure constraints. Thus H. azteca is probably a suitable surrogate species for determining sediments that are likely not toxic to field populations; however, it is not suitable for determining sediments that are likely toxic to field populations.

Amphipoda↗

Bioaccumulation of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene by mussels transplanted in a coastal lagoon.

The bioaccumulation of two isomeric non-alternant non-priority polycyclic aromatic hydrocarbons (PAHs), namely cyclopenta[cd]pyrene and benzo[ghi]fluoranthene, was investigated in caged mussels (Mytilus galloprovincialis) exposed for 30 days in three sites of a coastal lagoon (Pialassa Baiona, Ravenna, Italy) contaminated by pyrogenic PAHs. The concentration of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene increased from undetectable levels in reference mussels withdrawn from the Adriatic sea to 10-30 ng g(-1) dry weight in transplanted mussels. Other contaminants bioaccumulated by caged mussels included pyrene, fluoranthene and mercury. Whilst the isomer concentration ratio pyrene/fluoranthene in biota was comparable to that observed in sediments, the cyclopenta[cd]pyrene/benzo[ghi]fluoranthene ratio was much lower in mussels than in sediments. The lower sediment biota accumulation factor of cyclopenta[cd]pyrene with respect to that of benzo[ghi]fluoranthene was tentatively attributed to the greater biological activity of the former compound, which contains a reactive olefinic bond in the cyclopenta fused ring moiety. Given the higher mutagenic activity of cyclopenta[cd]pyrene with respect to other priority PAHs, its bioaccumulation from contaminated sediments may rise considerably the overall toxicity of PAH residues in exposed biota.

Animals↗