Toxicities of ten metals to Crassostrea gigas and Mytilus edulis embryos and Cancer magister larvae

Pacific oyster (Crassostrea gigas Thunberg) embryos, bay mussel (Mytilus edulis Linnaeus) embryos, and Dungeness crab (Cancer magister Dana) zoea I stage larvae were exposed to arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, and zinc salts. The two bivalve species were exposed through the completion of embryogenesis (48 h), and the effects of the metals upon abnormal development were monitored. The crab larval stages were exposed to the metal solutions for 96 h. Concentrations (μg l_.^?1 as metal) which caused 50% abnormal development in the two species of bivalve larvae and which were fatal to 50% of the crab larvae ranged from 5.3 (oyster) to 49 (crab) for copper; 5.8 (mussel) to 8.2 (crab) for mercury; 14 (mussel) to 55 (crab) for silver; 119 (oyster) to 456 (crab) for zinc; 232 (crab) to 3000 (mussel) for arsenic; 247 (crab) to 1200 (mussel) for cadmium; 349 (oyster) to 4360 (crab) for nickel; 476 (mussel) to 758 (oyster) for lead; 3440 (crab) to 4538 (oyster) for hexavalent chromium; and selenium greater than 10 000 for the three species. The acute toxicity testing of C. gigas embryo together with two California native species confirmed its usefulness for predicting toxicity to the latter species.     

Acute toxicity of heavy metals to some marine larvae

The toxicity of copper, mercury and zinc to the larvae of oysters, shrimp, crab and lobsters has been examined over periods of up to 64 hours. Mercury was found to be more toxic than copper and zinc, which had similar levels of toxicity. Over the experimental period, the relationship between toxicity and concentration was linear. Larvae were from 14 to 1,000 times more susceptible than adults of the same species. The median lethal concentrations (LC₅₀) of each metal to the most sensitive species of larvae, tested over a 48 hour period, exceeded the concentrations found in natural sea water by a factor of 100. For longer test periods, the LC₅₀ would be considerably less and this factor would then be considerably reduced. Hence the continued addition of these metals to confined waters should give cause for concern.     

Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay,Japan

Contaminations in sediments by polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs were investigated at 44 sites in Osaka Bay, Japan. Concentrations of total PAHs and alkylated PAHs were in the range 6.40–7800 ng/g dry weights and 13.7–1700 ng/g dry weights, respectively. The PAH concentrations tended to be higher along the shoreline in the vicinities of big ports, industrialized areas, and densely populated regions such as the cities of Osaka and Kobe. The major sources appeared to be pyrogenic or both pyrogenic and petrogenic at most of the sites. PAH concentrations were remarkably high at a site near Kobe, where the concentrations of dibenzo(a,h)anthracene and benzo(g,h,i)perylene exceeded the effects-range-medium concentration and eight PAHs were above the corresponding effects-range-low concentrations. Those PAHs may have been derived from the great fire associated with the large earthquake in 1995.     

Embryotoxic and genotoxic effects of heavy metals and pesticides on early life stages of Pacific oyster (Crassostrea gigas)

This study evaluated embryotoxicity and genotoxicity of two dissolved metals copper and cadmium (Cu and Cd) and two pesticides (metolachlor and irgarol) occurring in Arcachon Bay (SW France) in Pacific oyster (Crassostrea gigas) larvae and investigated the relationship between those two endpoints. Embryotoxicity was measured by calculating the percentage of abnormal D-shaped larvae and genotoxicity was evaluated with DNA strand breaks using the comet assay. After 24 h exposure, significant increases of the percentage of abnormal D-larvae and the DNA strand breaks were observed from 0.1 μg L⁻¹ for Cu, 10 μg L⁻¹ for Cd and 0.01 μg L⁻¹ for both irgarol and metolachlor in comparison with the controls. A strong positive relationship between embryotoxicity and genotoxicity was recorded for Cu, Cd and metolachlor. The current study suggests that copper, irgarol and metolachlor can induce larval abnormalities and DNA damage in a population of exposed oysters at environmentally relevant concentrations.     

Occurrence and fate of polycyclic aromatic hydrocarbons in the coastal surface microlayer

Polycyclic aromatic hydrocarbons (PAHs) were measured in the coastal sea surface microlayer (SML), the sub-surface waters (SSW) and the overlying atmosphere in order to investigate the influence of the SML on contaminant enrichment and air-sea exchange. Samples were collected at two contrasting locations of the NW Mediterranean, one urban influenced (off Barcelona, Spain) and another comparatively clean (off Banyuls-sur-Mer, France). Statistical data analysis confirmed the accumulation of PAHs in the SML with respect to the SSW (20.3+/-9.1 vs. 13.1+/-10.0 ng L(-1) in the dissolved phase; 709+/-207 vs. 158+/-111 ng g(-1) in the particulate phase). This accumulation was higher at the contaminated location (Barcelona station) compared with the more pristine one, with PAH enrichments 1.5 and 4.5 times higher for the dissolved and particulate phases, respectively, indicating that the enrichment of PAHs in the SML is dominated by particle transport processes.     

The distribution and sources of polycyclic aromatic hydrocarbons in Narragansett Bay surface sediments

Polycyclic aromatic hydrocarbons (PAHs) were measured in 41 surface sediments from Narragansett Bay, RI. All the analytes generally decrease down bay from the Seekonk, Providence and Taunton Rivers at the head of the bay. Total PAHs ranged from 0.569 to 216 microg/g with 27% exceeding the effects range median (ERM) of 44.8 microg/g and 73% of the stations exceeding the effects range low (ERL) of 4.02 microg/g (Long et al., 1995). Based on principal component analysis, the major source of the contaminants in Narragansett Bay was the Providence River while the coves and Taunton River/Mt. Hope Bay appeared to only have a limited influence on the open bay. PAH source ratios indicate that creosote and/or coal may be the most significant contributor of pyrogenic high molecular weight PAHs in Narragansett Bay, along with significant contributions from diesel exhaust.     

Bioconcentration of heavy metals in aquatic environments: the importance of bioavailability

The importance of heavy metal bioavailability on the bioconcentration in aquatic biota is examined. To this purpose, mono- and multivariate statistical techniques are applied to develop correlations between heavy metal bioconcentration factor and sediment characteristics, that are expected to affect bioavailability, using a database of heavy metal concentrations in biota and sediment along with the available physicochemical characteristics. The statistical analysis shows that satisfactory correlations are obtained only when factors that affect bioavailability, such as metal oxides concentration and organic carbon content in the sediment, are taken into account.     

Vertical profile,sources, and equivalent toxicity of polycyclic aromatic hydrocarbons in sediment cores from the river mouths of Kaohsiung Harbor,Taiwan

Six sediment cores collected at four contaminated river mouths and two harbor entrances in Kaohsiung Harbor (Taiwan) were analyzed to evaluate the sources and potential toxicity of polycyclic aromatic hydrocarbons (PAHs). PAHs presented the wide variations ranging from 369 ± 656 to 33,772 ± 14,378 ng g⁻¹ at the six sampling sites. The composition of PAHs presented a uniform profile reflecting the importance of atmospheric input from vehicle exhausts or coal combustion in the river mouths. PAHs diagnostic ratios indicated a stronger influence of coal combustion in the Salt River mouth and the prevalence of petroleum combustion and mixed sources in the other rivers and harbor entrances. PAHs toxicity assessment using the mean effect range-median quotient (m-ERM-q: 0.011–1.804), benzo[a]pyrene-toxicity equivalent (TEQ^carc: 22–2819 ng TEQ g⁻¹), and dioxin-toxicity equivalent (TEQ^fish: 37–5129 pg TEQ g⁻¹) identified the Salt River mouth near the industrial area of the harbor as the most affected area.     

Assessment of the Uvod Reservoir pollution with heavy metals

Concentrations of heavy metals (Cu, Ni, Cd, Pb, Cr, and Zn) in bottom sediments, water, snow, and biota of the Uvod Reservoir, as well as of rare-earth elements (Ce, Dy, Er, Eu, Gd, Ho, La, Lu, Nd, Pr, Sm, Tb, Y, and Yb) in its water are assessed. Geochemical studies of concentrations of Cu, Ni, Cd, Pb, Cr, and Zn in soils, water, and snow allow us to state that the metals enter the reservoir mostly from natural sources; however, some part of them are of anthropogenic origin. The sum of concentrations of light rare-earth elements (La, Ce, and Nd) make almost the total of all rare-earth elements in the reservoir—from 70 to 97%, depending on the sampling site. The highest concentrations of metals (and the highest percentage of their labile forms) are recorded in the Priplotinnyi and Kolbaskinskii (in macrophite deposits) pools and at the site of water inflow from the Volga-Uvod canal. There is also reason to suppose a secondary entry of the elements under study into the water mass. The largest variations in metals’ concentrations are observed during the periods of spring and autumn floods, when a great quantity of terrigenous suspended matter enters the water body. The distribution of the above metals and rare-earth elements in water is uneven; their highest concentrations are observed in the site of water inflow from the canal and in the Uvod River (the latter is likely to be due to the effect of the settlement of Pistsovo). The analysis of biota (fennel-leaved pondweed and zooplankton) has shown that the Uvod Reservoir is polluted with heavy metals.     

Isolation, characterization of Rhodococcus sp. P14 capable of degrading high-molecular-weight polycyclic aromatic hydrocarbons and aliphatic hydrocarbons

Rhodococcus sp. P14 was isolated from crude oil-contaminated sediments. This strain was capable of utilizing three to five rings polycyclic aromatic hydrocarbons (PAHs) including phenanthrene (Phe), pyrene (Pyr), and benzo[a]pyrene (BaP) as a sole carbon and energy source. After cultivated with 50mg/L of each PAH, strain P14 removed 43% Phe, 34% Pyr and 30% BaP in 30 d. Four different hydroxyphenanthrene products derived from Phe by strain P14 (1,2,3,4-hydroxyphenanthrene) were detected using SPME-GC-MS. Strain P14 also was capable of degrading mineral oil with n-alkanes of C17 to C21 carbon chain length. Compared with glucose-grown cells, PAHs-grown cells had decreased contents of shorter-chain length fatty acids (≤ C16:0), increased contents of C18:0, Me-C19:0 and disappeared odd-number carbon chain fatty acids. The contents of unsaturated C19:1, Me-C19:0 increased and C18:0 decreased in mineral oil-grown cells. At the same time, the strain P14 tended to float when cultivated in mineral oil-supplemented liquid medium. The degradation capability of P14 to alkane and PAHs and its floating characteristics will be very helpful for future's application in oil-spill bioremediation.     

Mass fraction spatiotemporal geostatistics and its application to map atmospheric polycyclic aromatic hydrocarbons after 9/11

This work proposes a space/time estimation method for atmospheric PM_2.5 components by modelling the mass fraction at a selection of space/time locations where the component is measured and applying the model to the extensive PM_2.5 monitoring network. The method we developed utilizes the nonlinear Bayesian maximum entropy framework to perform the geostatistical estimation. We implemented this approach using data from nine carcinogenic, particle-bound polycyclic aromatic hydrocarbons (PAHs) measured from archived PM_2.5 samples collected at four locations around the World Trade Center (WTC) from September 22, 2001 to March 27, 2002. The mass fraction model developed at these four sites was used to estimate PAH concentrations at additional PM_2.5 monitors. Even with limited PAH data, a spatial validation showed the application of the mass fraction model reduced the mean squared error (MSE) by 7–22%, while in the temporal validation there was an exponential improvement in MSE positively associated with the number of days of PAH data removed. Our results include space/time maps of atmospheric PAH concentrations in the New York area after 9/11.     

Assessment of polycyclic aromatic hydrocarbon input to urban wetlands in relation to adjacent land use

The relationship between polycyclic aromatic hydrocarbons (PAHs) in wetland surface sediments and adjacent land use was assessed in the Elizabeth River, VA, an urbanized sub-estuary of the Chesapeake Bay. Significant differences (p<0.05) in surface sediment PAH concentration between sites indicated adjacent land use had a substantial influence on PAH concentration in wetland sediments. Wetlands adjacent to parking lots and petroleum industrial sites exhibited the highest PAH concentrations of all wetlands examined. Overall, commercial land uses had the highest PAH concentrations and automotive sources dominated (52-69%) PAH input to wetland surface sediments irrespective of adjacent land use.     

Occurrence and distribution of polycyclic aromatic hydrocarbons in surface sediments of San Diego Bay marinas

Polycyclic aromatic hydrocarbons (PAHs) have garnered much attention due to their bioaccumulation, carcinogenic properties, and persistence in the environment. Investigation of the spatial distribution, composition, and sources of PAHs in sediments of three recreational marinas in San Diego Bay, California revealed significant differences among marinas, with concentrations in one site exceeding 16,000 ng g^? 1. ‘Hotspots’ of PAH concentration suggest an association with stormwater outfalls draining into the basins. High-molecular weight PAHs (4–6 rings) were dominant (> 86%); the average percentage of potentially carcinogenic PAHs was high in all sites (61.4–70%) but ecotoxicological risks varied among marinas. Highly toxic benzo(a)pyrene (BaP) was the main contributor (> 90%) to the total toxic equivalent quantity (TEQ) in marinas. PAHs in San Diego Bay marina sediments appear to be derived largely from pyrogenic sources, potentially from combustion products that reach the basins by aerial deposition and stormwater drainage from nearby streets and parking lots.     

Contamination and potential biodegradation of polycyclic aromatic hydrocarbons in mangrove sediments of Xiamen, China

Five stations were established in the Fenglin mangrove area of Xiamen, China to determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) and the numbers of PAH-degrading bacteria in surface sediments. Assessing the biodegradation potential of indigenous microorganisms and isolating the high molecule weight (HMW)-PAH degrading bacteria was also one of the aims of this work. The results showed that the total PAH concentration of sediments was 222.59 ng g(-1) dry weight, whereas the HMW-PAH benzo(a)pyrene (BaP) had the highest concentration among 16 individual PAH compounds. The variation in the numbers of PAH-degrading bacteria was 2.62 x 10(2)-5.67 x 10(4)CFU g(-1) dry weight. The addition of PAHs showed a great influence in increasing the microbial activity in mangrove sediments. A bacterial consortium, which could utilize BaP as the sole source of carbon and energy, and which was isolated from mangrove sediments and enriched in liquid medium for nearly one year degraded 32.8% of BaP after 63 days incubation.     

白洋淀沉积物重金属潜在生态风险及生物可利用性分析

沉积物是湖泊水体重金属的主要汇集场所,也是湖泊重金属污染研究及整治的重点.本文分析了白洋淀多个淀区沉积物中16种重金属含量水平及垂向分布特征,解析了其中典型有害重金属潜在生态风险,并基于酸可挥发性硫（AVS）及同步可提取金属（SEM）、间隙水溶解态金属、可转化态金属形态分级等研究,对重金属生物可利用性进行了分析.结果表明：沉积物重金属含量均值高低依次为Fe （29630.50 mg/kg）>Ti （3213.07 mg/kg）>Mn （539.44 mg/kg）>Zn （104.01 mg/kg）>V （76.63 mg/kg）>Cr （52.60 mg/kg）>Cu （43.49 mg/kg）>Ni （35.83 mg/kg）>Pb （26.75 mg/kg）>Co （10.32 mg/kg）>As （8.96 mg/kg）>Mo （2.06 mg/kg）>Sb （1.57 mg/kg）>Tl （0.43 mg/kg）>Cd （0.31 mg/kg）>Hg （0.16 mg/kg）;其中,10种重金属在各淀区沉积物中呈现出自北往南逐渐降低的趋势,各金属在不同淀区分布差异性主要由污染输入所致.除北部烧车淀区域外,其余区域重金属潜在生态风险总体处于较低水平.重金属污染主要来源于该区域周边河道,但近10年来污染输入及在沉积物中的富集总体趋于稳定并呈逐渐降低的趋势.入淀污染不仅增加了该区域沉积物中重金属总量,也使得其中可转化态重金属比例较高,大多在30%~90%之间,提升了重金属生物可利用潜力.水生植物等内生性有机质的大量富集导致沉积物还原性较强,AVS含量较高,沉积物中AVS和ΣSEM均值分别为（10.59±6.37）和（2.23±1.53）μmol/g （dw）.Cd、Cu、Ni、Pb、Zn等金属由于高含量还原态硫的固定而生物可利用性较低.然而,As和Hg在这样的高有机质和强还原环境下更容易溶解和释放,是潜在生物可利用性相对较高的金属,在间隙水中的浓度分别达到（17.07±0.23）和（2.39±0.94）μg/L,未来研究及整治中应给予更多关注.     

Chemical speciation of polycyclic aromatic hydrocarbons in sediments: Partitioning and extraction of humic substances

The primary objective of this study was to examine the chemical speciation of polycyclic aromatic hydrocarbons (PAHs) found in sediments endowed with different characteristics. To achieve this purpose and because the nature of the sediments influences the distribution of PAHs, we have analyzed four different types of sediments. To study the role of organic matter in the sequestration of PAHs, we fractionated humic substances into humic acids and humin-mineral fractions. After their separation and purification, the humic components were examined for their sorptive reactivity by extracting them with organic solvents; these extracts were subsequently subjected to GC/MS analysis. Our results show that PAHs are distributed between labile and sequestered fractions in sediments. A slower uptake of PAHs occurs when the sequestered fraction is formed, and this process can be prolonged and may be influenced by the characteristics if the sediment. Our study suggests that organic contaminants are available in muddy sediments for a longer period of time than in sandy sediments.