Research on heavy metals in Ruditapes philippinarum and soda industry wastes

Heavy metals pollution in Jiaozhou Bay was studied inRuditapes. philippinarum, a bioindicator of seawater pollution. Heavy metals in soda industry wastes “white mud” were also studied. Comparison of microwave digestion method with general digestion method revealed that microwave digestion is superior to general digestion in precision, recovery, digestion speed and efficiency, etc. Cd concentration in HongdaoR. philippinarum samples exceeded the national standard by 0.046 mg/kg, that of Yinghai sample by 0.02 mg/kg, and that of Hongshiya sample by 0.22 mg/kg. Sample Pb concentration in Hongshiya was found to exceed the national standard by 0.02 mg/kg. However the heavy metals concentration inR. philippinarum near the Qingdao Alkaline Factory was complied with the standard. This was proved byPenaeus chinensis culture experiment. Therefore, the possible contamination source may come from other land areas. This study is supported by Project 973 (NO.2002CB 412402), and key project of the Chinese Academy of Sciences (Grant NO.KJCX315W-215).     

Accumulation of petroleum hydrocarbons and heavy metals in clams （Ruditapes philippinarum） in Jiaozhou Bay, China

Accumulation and distributions of aliphatic and polyaromatic hydrocarbons (PAHs) and heavy metals were measured in tissues of the clam Ruditapes philippinarum collected from 5 sites in Jiaozhou Bay, Qingdao, China. The concentrations of total aliphatic hydrocarbon and PAHs ranged from 570 to 2 574 ng/gdw (gram dry weight) and from 276 to 939 ng/gdw, in the most and least polluted sites, respectively. The bio-accumulation of hydrocarbons and PAHs in the clams appeared to be selective. Aliphatic hydrocarbons were predominantly represented by short chain (<nC₂₃) n-alkanes, suggesting that petroleum hydrocarbons were likely the major contamination source. The selective uptake of 3 and 4 ring PAHs, such as naphthalene, fluorene, phenanthrene, fluoranthene and pyrene, by the clams was probably related to the physiological and bio-kinetic processes that were energetically favorable for uptake of compounds with fewer rings. Accumulation of the metals Cd, Cu, Zn, Pb, Cr, Hg, and As in the clam tissues also showed high variability, ranging from 0.043 to 87 μg/gdw. Among the 7 detected metals, Zn, Cd, Cu, and As had a particularly high potential of accumulation in R. philippinarum. In general, a positive correlation was found between the tissue concentrations and sediment concentrations of hydrocarbons and of some metals. Our study suggests that moderate contamination with polyaromatic hydrocarbons, and low to moderate contamination with metals, currently exists for clam R. philippinarum in Jiaozhou Bay, in comparison with other regional studies. A long-term monitoring program is certainly needed for assessment of the potential ecological influence and toxicity of these contaminants of R. philippinarum in Jiaozhou Bay.     

Annual variations of biogenic element contents of manila clam (Ruditapes philippinarum) bottom-cultivated in Jiaozhou Bay,China

Manila clam(Ruditapes philippinarum) was monthly sampled from its benthic aquaculture area in Jiaozhou Bay from May 2009 to June 2010. The annual variations of major elemental composition, organic content, fatness and element ratio of Manila clam were examined. The element removal effect of clam farming in Jiaozhou Bay was analyzed based on natural mortality and clam harvest. The results indicated that the variation trend of carbon content in shell(Cshell) was similar to that in clam(Cclam). Such a variation was higher in summer and autumn than in other seasons, which ranged from 9.10 ± 0.13 to 10.38 ± 0.09 mmol g-1 and from 11.28 ± 0.29 to 12.36 ± 0.06 mmol g-1, respectively. Carbon content of flesh(Cflesh) showed an opposite variation trend to that of shell in most months, varying from 29.42 ± 0.05 to 33.64 ± 0.62 mmol g-1. Nitrogen content of shell(Nshell) and flesh(Nflesh) changed seasonally, which was relatively low in spring and summer. Nshell and Nflesh varied from 0.07 ± 0.009 to 0.14 ± 0.009 mmol g-1 and from 5.46 ± 0.12 to 7.39 ± 0.43 mmol g-1, respectively. Total nitrogen content of clam ranged from 0.50 ± 0.003 to 0.76 ± 0.10 mmol g-1 with a falling tend except for a high value in March 2010. Phosphorus content of clam(Nclam) fluctuated largely, while phosphorus content of shell(Pshell) was less varied than that of flesh(Pflesh). Pshell varied from 0.006 ± 0.001 to 0.016 ± 0.001 mmol g-1; while Pflesh fluctuated between 0.058 ± 0.017 and 0.293 ± 0.029 mmol g-1. Pclam ranged from 0.015 ± 0.002 to 0.041 ± 0.006 mmol g-1. Carbon and nitrogen content were slightly affected by shell length, width or height. Elemental contents were closely related to the reproduction cycle. The removal amounts of carbon, nitrogen and phosphorus from clam harvest and natural death in Jiaozhou Bay were 2.92×104 t, 1420 t and 145 t, respectively. The nutrient removal may aid to reduce the concentrations of nitrogen and phosphorus, the main causes of eutrophication, and to maintain the ecosystem health of Jiaozhou Bay.     

Acid volatile sulfide and simultaneously extracted metals in tidal flat sediments of Jiaozhou Bay,China

It is well known that acid-volatile sulfide （AVS） plays an important role in influencing the toxicity of divalent cationic metals within anoxic sediments. In studying sediment core samples collected from tidal flats within the Jiaozhou Bay, China, we found that the AVS concentration gradually increases with depth and decreases from high tidal flat to low tidal flat areas. We evaluated the chemical activity and bioavailability of heavy metals in the tidal flat based on the molar ratio of simultaneously extracted metals （SEM） and AVS. The value of SEM/AVS is generally less than 1 in this area except for the surface layer, which suggests that the heavy metals only have chemical activity in the surface layer. SEM is most highly concentrated at the boundary of the redox layer SEM have similar depth distributions throughout the tidal flat. The aeration of low tidal flat sediment indicates that SEM gradually move to deeper sites via interstitial water.     

Pb distribution and translocation in Jiaozhou Bay

The trends of distribution, translocation and seasonal change of heavy metal Pb were studied based on the surface and bottom water sampling in Jiaozhou Bay in 1979, and compared with those in 1990＇s. The results showed that the source of Pb in the bay was from wastewater and sewage in the east of Jiaozhou Bay from ocean vessels. Pb concentration was higher in spring and lower in summer and autumn, and remained stable through sedimentation in the bottom layer. The overall water quality was good in 1970＇s. Compared with the environmental monitoring data of 1995-1999, Pb pollution had become serious. Therefore, more efforts should be made to protect the bay from Pb pollution.     

Observations on shell growth and morphology of the bivalve Ruditapes philippinarum

The bivalve Ruditapes philippinarum is not only one of the main mollusc species in the west Pacific Ocean, but also one of the main species for aquaculture in China. Knowledge of growth of the R. philippinarum shell will improve our understanding of the shell as an environmental archive. It is also useful for the aquaculture of R. philippinarum. In this research, a hanging box culture method was introduced in the culture of R. philippinarum. The bivalves were cultured for 126 days, from March 31 to August 3, 2002. The average growth rates of shell width, height, and thickness were 0.069, 0.046, and 0.032 mm/d, respectively. The mean increase of average individual wet mass was 0.028 g/d. The largest growth rates of both shell and average individual wet mass occurred in June, indicating that water temperature and bivalve reproduction were 2 important factors. The shell morphology underwent significant changes with shell growth. The ratio of height to thickness (value of B/C) shifted 1.58 in the first 60 days to 1.54 in the last 30 days, which was resulted from the change in major shell growth direction. Periodic changes in the B/C ratio led to corrugated shell form, which could be used to determine the age of the shell.     

The influence of salinity on toxicological effects of arsenic in digestive gland of clam Ruditapes philippinarum using metabolomics

Ruditapes philippinarum,a clam that thrives in intertidal zones of various salinities,is a useful biomonitor to marine contaminants.We investigated the influence of dilution to 75% and 50% of normal seawater salinity(31.1) on the responses of the digestive gland of R.philippinarum to arsenic exposure(20 μg/L),using nuclear magnetic resonance(NMR)-based metabolomics.After acute arsenic exposure for 48 h,salinity-dependent differential metabolic responses were detected.In normal seawater,arsenic exposure increased the concentrations of branched-chain amino acids,and of threonine,proline,phosphocholine and adenosine,and it decreased the levels of alanine,hypotaurine,glucose,glycogen and ATP in the digestive glands.Differential changes in metabolic biomarkers observed at lower salinity(～23.3) included elevation of succinate,taurine and ATP,and depletion of branched-chain amino acids,threonine and glutamine.Unique effects of arsenic at the lowest salinity(～15.6) included down-regulation of glutamate,succinate and ADP,and up-regulation of phosphocholine.We conclude that salinity influences the metabolic responses of this clam to arsenic.     

THE RESEARCH ON THE DISTRIBUTION AND FORMS OF HEAVY METALS IN THE XIANGJIANG RIVER SEDIMENTS

In this paper, the contents and various forms of Cd, Cu, Zn and Pb in the sediments of the Xiangjiang River have been investigated. The presentation of this paper focuses on the various forms and characteristics of the heavy metals in the column sediments at Xiawan Port of Zhuzhou, which has been severely polluted by a metallurgical plant.The forms of the heavy metals discussed in this paper are: The concentration of the exchangeable forms of Cd, Cu, Zn and Pb, in the forms of carbonates and Fe/ Mn oxide in water, the combination of Cu with organic matter and form, and the proportion of the residue form at each section have been studied.     

Spatial distribution and changes of heavy metals of agricultural lands in typical pregrading coast in Dongtai City,Jiangsu Province,China

According to the historical changes of coastal lines, seven soil sampling districts, from land to sea, were arranged in Dongtai City, Jiangsu Province to sample soils from surface and profile. Concentrations of seven major heavy metals （HMs）, granularity, pH, organic matters and C/N of the soil samples were analyzed. Results show that concentrations of heavy metals in agricultural land present a certain spatial variance, decreasing from land to sea. Pollution assessment indicates that the agricultural soils were not polluted by HMs, but the potential pollution of Cu and Hg needs to be alerted. Different HMs accumulate in the surface and sub-surface of the soil profiles, and concentrations of Hg and Pb decrease significantly with the increment of soil depth. Concentrations of HMs exhibit a significantly negative correlation to pH, but have no significant relation with organic matters in soil. Principle component analysis show that the concentrations of HMs relate to the land use history. Concentrations of Hg, Ni and Cr in soil are closely related with land use history, and concentrations of Pb, Cu and Cr are affected by land use history as well as other factors. However, there is no significant relation between concentration of As and land use history.     

Assessment of heavy metal pollution in estuarine surface sediments of Tangxi River in Chaohu Lake Basin

A total of 30 surface sediments samples from the estuary wetland of the Tangxi River, Chaohu Lake Basin were obtained and tested. Enrichment factor (EF) and geoaccumulation index (I_(geo)) as well as multivariate statistical analysis methods including Factor Analysis (FA) and Hierarchical Cluster Analysis (HCA) were applied for the assessment of heavy metal pollution in surface sediments. The results of EF values show that the pollution of copper (Cu) and cadmium (Cd) occurs in the estuarine sediments, and that zinc (Zn), lead (Pb) and chrome (Cr) may originate from crustal materials or natural weathering process. The mean EF values of the five heavy metals are in the decreasing order: Cu>Cd>Zn>Pb>Cr. Based on the I_(geo) of target heavy metals, the surface sediments collected from the study area can be approximately categorized as unpolluted with Zn, Pb and Cr, and moderately polluted with Cu and Cd. The degree of heavy metal pollution decreases in the order of Cu>Cd>Zn>Pb>Cr. Three groups of pollution factors are presented from FA: Zn-TOC, Cu-Cd and Cr-Pb, which respectively accounte for 27.22%, 25.20% and 21.05% of variance. By means of HCA, a total number of seven groups are distinguished from 30 sampling sites. Results indicate that Cu and Cd are the prior controlled pollutants in the estuarine sediments of the Tangxi River.     

Heavy metal concentration and its evaluation in the organisms from Meizhou Bay

The present paper reports Zn,Cu,Pb,Cd,Ni,Fe,Mn and Co contents in the tissues of oyster,solen,red-tail prawn,sea eel and kelp,taken from Meizhou Bay(and analysed by flame atomicabsorption spectrophotometry after wet digestion)in June 1992,and also the concentration factors esti-mated from the mean metal concentrations in the organisms and water there.Heavy metal concentrationsin every species of the organisms followed the pattern:Fe,Mn,Cu,Zn>Pb,Cd,Ni,Co and in variousorganisms showed considerable variation.In general,levels of most of these metals were in the order:softtissues of the bivalves>the kelp>muscles of the red-tail prawn,the sea eel.The greatest concentrationof most metals was found in the gill or viscera of the sea eel,whereas the muscle tissues,in general,con-tained only low concentrations of them.The Cu,Zn concentration factors of the oyster were higher by1—2 orders of magnitude than that of the other organisms.The observed heavy metal levels were closeto those reported from various waters     

Molecular cloning and differential expression patterns of sigma and omega glutathione S-transferases from <Emphasis Type="Italic">Venerupis philippinarum</Emphasis> to heavy metals and benzo[a]pyrene exposure

Glutathione S-transferases (GSTs) are a class of enzymes that facilitate the detoxification of xenobiotics, and also play important roles in antioxidant defense. We identified two glutathione S-transferase isoforms (VpGSTS, sigma GST; VpGSTO, omega GST) from Venerupis philippinarum by RACE approaches. The open reading frames of VpGSTS and VpGSTO were of 612 bp and 729 bp, encoding 203 and 242 amino acids with an estimated molecular mass of 22.88 and 27.94 kDa, respectively. The expression profiles of VpGSTS and VpGSTO responded to heavy metals and benzo[a]pyrene (B[a]P) exposure were investigated by quantitative real-time RT-PCR. The expression of VpGSTS and VpGSTO were both rapidly up-regulated, however, they showed differential expression patterns to different toxicants. Cd displayed stronger induction of VpGSTS expression with an approximately 12-fold increase than that of VpGSTO with a maximum 6.4-fold rise. Cu exposure resulted in similar expression patterns for both VpGSTS and VpGSTO. For B[a]P exposure, the maximum induction of VpGSTO was approximately two times higher than that of VpGSTS. Altogether, these findings implied the involvement of VpGSTS and VpGSTO in host antioxidant responses, and highlighted their potential as a biomarker to Cd and B[a]P exposure.     

Silicon limitation on primary production and its destiny in Jiaozhou Bay, China——Ⅳ：Study on cross-bay transect from estuary to ocean

The authors analyzed the data collected in the Ecological Station Jiaozhou Bay from May 1991 to November 1994, including 12 seasonal investigations, to determine the characteristics, dynamic cycles and variation trends of the silicate in the bay. The results indicated that the rivers around Jiaozhou Bay provided abundant supply of silicate to the bay. The silicate concentration there depended on river flow variation. The horizontal variation of silicate concentration on the transect showed that the silicate concentration decreased with distance from shorelines. The vertical variation of it showed that silicate sank and deposited on the sea bottom by phytoplankton uptake and death, and zooplankton excretion. In this way, silicon would endlessly be transferred from terrestrial sources to the sea bottom. The silicon took up by phytoplankton and by other biogeochemical processes led to insufficient silicon supply for phytoplankton growth. In this paper, a 2D dynamic model of river flow versus silicate concentration was established by which silicate concentrations of 0.028–0.062 μmol/L in seawater was yielded by inputting certain seasonal unit river flows (m³/s), or in other words, the silicate supply rate; and when the unit river flow was set to zero, meaning no river input, the silicate concentrations were between 0.05–0.69 μmol/L in the bay. In terms of the silicate supply rate, Jiaozhou Bay was divided into three parts. The division shows a given river flow could generate several different silicon levels in corresponding regions, so as to the silicon-limitation levels to the phytoplankton in these regions. Another dynamic model of river flow versus primary production was set up by which the phytoplankton primary production of 5.21–15.55 (mgC/m²·d)/(m³/s) were obtained in our case at unit river flow values via silicate concentration or primary production conversion rate. Similarly, the values of primary production of 121.98–195.33 (mgC/m²·d) were achieved at zero unit river flow condition. A primary production conversion rate reflects the sensitivity to silicon depletion so as to different phytoplankton primary production and silicon requirements by different phytoplankton assemblages in different marine areas. In addition, the authors differentiated two equations (Eqs. 1 and 2) in the models to obtain the river flow variation that determines the silicate concentration variation, and in turn, the variation of primary production. These results proved further that nutrient silicon is a limiting factor for phytoplankton growth. This study was funded by NSFC (No. 40036010), and the Director's Fund of the Beihai Sea Monitoring Center, the State Oceanic Administration.     

湛江港湾表层沉积物重金属的分布特征及潜在生态危害评价

利用双道原子荧光分析仪对湛江港附近海域表层沉积物砷、汞、铅、镉的含量进行了分析,阐明了这几种重金属的分布特征。结果表明,As的质量分数为(8.138~16.749)×10-6,平均12.745×10-6;Hg的质量分数为未检出(nd)~0.322×10-6,平均0.059×10-6;Pb的质量分数为(14.306~68.904)×10-6,平均44.258×10-6;Cd的质量分数为(1.561~6.882)×10-6,平均3.0874×10-6;砷、汞、铅从港内往港外有逐渐减少的趋势,镉的分布没有规律性,在整个港湾内的分布较均匀。从单因子污染指数看,砷、汞和铅都属生态危害轻微;镉污染较为严重,属生态危害强;从综合污染指数看,属生态危害中等。     

Source of and potential bio-indicator for the heavy metal pollution in Ny-(A)lesund, Arctic

Three kinds of tundra plant samples including Dicranum angnstum(a type of boreal bryophyte) , PuccineUia phryganodes (a type of fringy p/ant),Salix polaris (a type of vascular plant) and surface soil were samples in 200 at Ny-Alesund of the Arctic.The levels of eight heavy metal elements (Hg, Pb, Cd, Cu, Zn, Ni, Fe and Mn) and three metal-like dements (As, Se, Sr) in the plant and soil samples of the areas within previous coal mining activities are significantly higher than those of other areas.The relative accumulation of these elements in these tundra plant samples is consistent with the one in the soft samples, especially in the areas affected by previous coal-mining activities.Thus, the pollution is apparently from local coal mining activity.Dicranum angustum has the highest concentrations among those elements, and it can be a good bio-indicator for heavy metal pollution in Ny(A)lesund.Though Ny(A)lesund is less polluted by heavy metal than nearby Northern European human living areas, but much more than the tundras of the Alaska, Greenland and the Antarctic.     

Distribution and accumulation characteristics of heavy metals in sediments in southern sea area of Huludao City, China

The southern sea area of the Huludao City, Liaoning Province might be polluted by heavy metals because it is close to the Jinzhou Bay, one of the heaviest sea area polluted by heavy metals in China. The undisturbed modern sediment core can be used to analyze the accumulation and source of the pollutants using 137 Cs and 210 Pb ex . Thirty-five samples of surface sediment and two core sediments were collected from the southern sea area of Huludao City. The concentrations of copper (Cu), lead (Pb), chrome (Cr), zinc (Zn), arsenic (As) and mercury (Hg) in the surface sediments as well as Cu, Pb, Zn, Cr, 137 Cs and 210 Pb ex in the core sediments were determined to research the spatial distribution and accumulation characteristics, and to analyze the sources and the potential risks of heavy metals. The results show that the pollution levels of Zn and Hg are serious, and 26 stations are at moderate or heavy ecological risks. The concentrations of the heavy metals increase from east to west, as well as from open sea to offshore marine area. The concentrations of heavy metals are not high in the sediments adjacent to the Jinzhou Bay, and the influence caused by the seawater exchange with the Jinzhou Bay is little. The concentrations of the heavy metals in the core sediments show low-high-low characteristic, and it coincides with the pollution history of Huludao City. The atmospheric deposition of heavy metals from the Huludao Zinc Plant is likely to be the main source of pollution without direct discharge of wastewater. The high concentrations of heavy metals appear on the upper sediment of 20 cm. The shallow sediment with high heavy metal contents might be exposed to surface when it was disturbed by the ocean engineering and big storm surge, then cause risk to the safety of aquaculture and human healthy.     

STUDY ON PREDICTION FOR TRANSPORT AND DIFFUSION OF DREDGED MATYER IN JIAOZHOU BAY, CHINA

The finite-element method was used to simulate the currents of Jiaozhou Bay and the nearcoast areas, and then established the model of the transport and diffusion of suspended particulate matter there. The transport and diffusion of dredged matter near the discharging field were estimated ; and the results were used to analyze the effects of the suspended particulate matter on the marine environment.     

济南西部地区不同类型污染源作用下土壤各类元素含量特征及选择性种植浅析

通过分析研究区不同类型污染源条件下各类土壤元素含量的顺序,认为重金属在各类污染源土壤剖面中含量的顺序主要为:垃圾堆放污染类污水排放污染类禽畜粪便污染类;水溶性相对较强的K+,Mg2+,Na+,Cl-,SO2-4等离子,受污水排放类污染的影响明显,含量顺序为:污水排放污染类禽畜粪便污染类垃圾堆放污染类;NO-3在土壤中含量的顺序为:禽畜粪便污染类污水排放污染类垃圾堆放污染类;土壤主要常量养分在土壤中含量的顺序为:污水排放污染类垃圾堆放污染类禽畜粪便污染类。选择性种植的观点认为,在土壤肥力充足但重金属元素富集的土地,选择对该重金属元素富集较少的蔬菜(瓜果)进行种植,一方面充分利用了土壤肥力,另一方面较好地规避了重金属对作物的污染。     

Distribution of heavy metals and nutrients in rainwater in coastal regions between the southern Yellow Sea and East China Sea

Rainwater samples were collected in series in Qianliyan Island (southern Yellow Sea) and Shengsi Archipelago (East China Sea) between May 2000 and May 2002, chemical analysis for pH values,concentrations of heavy metals (Cu, Pb, Zn and Cd) and nutrients (NH4^-, NO3^-, PO43^-, SiO32^-) were performed.Results indicate that concentrations of most of the heavy metals and nutrients in rainwater show clear seasonal variation, i.e. high level in winter and low level in summer. Regionally, concentrations are higher in the southern Yellow Sea than in the East China Sea, but the annual input of heavy metals into oceans by wet deposition is similar in both stations. However, the input of nutrients by wet deposition in the East China Sea is 2-3 times higher than that in the southern Yellow Sea. In individual, Pb and PO4^3- are input to the sea mainly by dry deposition; whereas Cu, Zn, Cd and N compounds are input dominantly by wet deposition, the N/P ratios in the rainwater from two stations are much higher than those in seawater, showing a significant impact of atmospheric wet deposition on marine production and biogeochemical circulation of nutrients in these sea regions.