THE ESTUARINE CHEMISTRY OF THE ZHUJIANG RIVER I. TRACE METAL SPECIES IN WATER PHASE

Nine chemical species of Zn, Cd, Pb and Cu in the Zhujiang River estuary were measured by using the technique of ion-exchange, ultraviolet irradiation and anodic stripping voltammetry. According to the distribution of the nine species in percentage an estuarine chemical pattern of the metal elements Zn, Cd, Pb and Cu in the Zhujiang River estuary was roughly made, and it is suggested that this estuary has relatively great self purifying ability in respect to heavy metal pollution.     

Spatial structure and land use control in Extended Metropolitan Region of Zhujiang River Delta,China

The Zhujiang (Pearl) River Delta is one of the most developed Extended Metropolitan Regions (EMR) in China.With the rapid urbanization,the agglomeration of population and industries has emerged,which has led to dramatic changes of spatial structure and land use in this region.With data of high resolution TM remote sensing images and Google Earth maps,this paper identified and analyzed the spatial pattern of the Zhujiang River Delta EMR using Envy and ArcGIS tools.It was found that 1) the industrial land uses were expanding substantially,particularly on the bank sides of the Zhujiang River estuary;2) large-scale housing developments were concentrated in the fringe of metropolitan areas such as those of Guangzhou and Shenzhen;3) a regional transportation network with the spatial pattern of ″1 circle +2 pieces + 3 axes″ had significantly affected the location choice of manufacture enterprises.At the same time,both highly specialized land use and severely mixed land use patterns were identified.As a consequence of the latter,land use efficiency of the whole EMR areas was reduced.Moreover,ecologic and environmental problems were severe.Based on the above analysis,suggestions were given from the viewpoint of spatial safety,land use efficiency,and the reorganization of spatial structure in the Zhujiang River Delta EMR.     

Distribution Patterns of Major and Trace Elements and Provenance of Surface Sediments on the Continental Shelf off Western Guangdong Province and Northeastern Hainan Island

A coupled approach based on grain size and geochemical elements is used to trace the provenance of surface sediments and to confirm the distribution patterns of grain size and elements on the continental shelf off western Guangdong Province and northeastern Hainan Island. The mean grain size ranges from 0.05 φ to 7.28 φ with a mean value of 5.60 φ. The average concentrations of major elements descend in the order of SiO_2Al_2O_3CaOFe_2O_3K_2OMgONa_2OTiO_2 P_2O_5 MnO, while those of trace elements exhibit a descending order of Sr Rb Zn V Cr Pb Ni Cu As Cd. On the basis of the distribution patterns of elements and results of statistical analysis, the study area is classified into three zones. Zone I locates on the continental shelf off western Guangdong Province, and the sediments are mainly from Pearl River, Taiwanese rivers, and small rivers nearby. Zone II locates in the eastern exit of Qiongzhou Strait and the coastal area off Leizhou Peninsula, and the sediments are mainly from the erosion products of Qiongzhou Strait and Hainan Island. Zone III locates off the eastern Hainan Island and the continental shelf deeper than-50 m isobaths, and the sediments are mainly from Hainan Island and coral reef. The influence from open water should also be considered. Results indicate that the grain size is the main controlling factor for major and trace element contents and that anthropogenic impact and biological activity also play an important role in the distribution of these elements.     

Assessment of heavy metals in sediment in a heavily polluted urban river in the Chaohu Basin,China

The Nanfei River(Anhui Province,China) is a severely polluted urban river that flows into Chaohu Lake.In the present study,sediments were collected from the river and analyzed for their heavy metal contents.Multivariate statistics and the fuzzy comprehensive assessment method were used to determine the sources of pollution,the current pollution status,and spatial and temporal variations in heavy metal pollution in sediments.The concentrations of arsenic(As),cadmium(Cd),chromium(Cr),copper(Cu),mercury(Hg),nickel(Ni),lead(Pb),and zinc(Zn) in sediments ranged from 5.67–113,0.08–40.2,41.6–524,15.5–460,0.03–4.84,13.5–180,18.8–250,and 47.9–1 996 mg/kg,and the average concentrations of each metal were 1.7,38.7,1.8,5.5,18.8,1.3,2.5,and 11.1 times greater than the background values,respectively.Multivariate statistical analysis demonstrated that Hg,Cu,Cr,Cd,and Ni may have originated from industrial activities,whereas As and Pb came from agricultural activities.The fuzzy comprehensive assessment method,based on the fuzzy mathematics theory,was used to obtain a detailed assessment of the sediment quality in the Nanfei River watershed.The results indicated that the pollution was moderate in the downstream tributaries of the Nianbu and Dianbu Rivers,but was severe in the main channel of the Nanfei River and in the upstream tributaries of the Sili and Banqiao Rivers.Therefore,sediments in the Nanfei River watershed are heavily polluted and urgent measures should be taken to remedy the status.     

BACKGROUND STUDY ON NON-RESIDUAL PHASE OF ELEMENTS IN CHANGJIANG AND HUANGHE ESTUARINE SEDIMENTS

Analysis of Zn, Cu, Pb, Co, Cr, Li, Ni, K, Al, Fe extracted by 1 mol/L HCl or 0.5 mol/LHCl/H_2O_2, showed concentrations of Zn, Cu, Pb, Co, Cr, Fe, Ni were significantly correlated with Li, Al,K, and clay. Two methods are used to indicate the background value of the non-residual phase of elementsin sediments, and are the same as the methods used to indicate the background value of totalconcentrations in sediments. The first method uses correlograms and regression equations,the second usesthe mean element concentrations normalized with grain size. Li, Al, K can be used as reference elements to determine the background value of Zn, Cu, Pb, Co,Cr, Ni, Fe, while the clay concentration's correlation with some extractable concentrations can be used tocalculate the background value of the non-residual phase of elements as a percentage of clay concentrationin the sediments. Based on this study, the concept of using the background value of the non-residualphase of elements to compare the pollution level in differ     

Clay minerals and geochemistry of the bottom sediments in the northwestern East China Sea

Clay minerals of 34 sediments collected from the northwestern continental shelf of the East China Sea have been determined by X-ray diffraction analysis. The clay mineral distribution is mainly controlled by the sediment source and the dominant circulation pattern. The predominant clay mineral in our study area is illite comprising more than 67% of the whole clay fraction. The highest concentration of illite (>68%) is found in the southeastern offshore parts beyond the reach of terrigenous input from the Jeju Island. It means that these illites are largely transported by the Kuroshio Current from the South China Sea (SCS). Smectite is highly concentrated in the northwest middle part and in the outer-shelf mud patch. It seems to be due to the high supply of smectite transported from China where fine-grained sediments are discharged from modern and ancient Huanghe (Yellow) River. The relatively high abundant kaolinite is likely derived from the Changjiang (Yangtze) River via the Taiwan Warm Current. In contrast, large amounts of chlorite and high chlorite/kaolinite ratios occur in the northwestern area, reflecting the transportation by the Yellow Sea Coastal Current from the southern Yellow Sea. The discrimination diagrams clearly show that the sediments in the northwestern East China Sea are ultimately sourced from Chinese rivers, especially from the Huanghe River, whereas the sediment in the northeast part might come from the Jeju Island. The muddy sediments of the Changjiang River’s submerged delta have much lower 87Sr/86Sr ratios (0.716 2–0.718 0) than those of the Shandong Peninsular mud wedge (0.721 6–0.724 9), which are supposed to be originated from the Huanghe River, suggesting the distribution pattern of 87Sr/86Sr ratios as a new tracer to discriminate the provenance of shelf sediments in the study area. The 87Sr/86Sr ratios of the outer-shelf muddy sediments ranged from 0.7169 to 0.7216 in a wide range and was between those of the Huanghe River and Changjiang River sediments, suggesting multiple sources of the sediment in the area.     

Tracing the provenance of aeolian loess in the Yangtze River Delta through zircon U–Pb age and geochemical investigations

Given the conflicts over the proposed formation mechanisms of Xiashu loess, the question of the provenance of sediments comprising the Xiashu loess in the Yangtze River Delta has not been satisfactorily resolved. In this study, the provenance of aeolian sediments of the Yangtze River Delta, China was examined by applying the detrial zircon U–Pb dating technique, Sr–Nd isotopic and trace element compositional analysis. U-Pb dating analysis was conducted on the Xiashu loess at three locations over the Yangtze River Delta, including Huangnishan(HNS) hill, Shengshan(SS) island and the Xuancheng(XC) area. The Xiashu loess and the sediments of the Yangtze River Valley share considerable similarity in their zircon U-Pb age spectra with the same main age peak and comparable age distribution. By contrast, significant differences in the age spectra, existbetween the Xiashu loess and loess deposits of Chinese Loess Plateau(CLP). Coarse grains of the Yangtze River Delta loess may have a proximal material source identical to the sediments from the Yangtze River valley. Sr–Nd isotopic values of the Xiashu loess match those from the northern margin of the Tibetan Plateau. Rare earth element ratios independent of grain size illustrate that the values from loess of the Yangtze River Delta mostly overlap with those of CLP loess. This feature implies that loess from the Yangtze River Delta has a dominant source of distant material similar as the CLP loess. As such, we conclude that multi-proxy analysis of sediments can shed new light on tracing the provenance of aeolian loess in the Yangtze River Delta.     

Short-and long-term sediment transport in western Bohai Bay and coastal areas

Sediment cores (~40–100 cm) were collected at 12 locations in the western Bohai Bay, the Haihe River estuary, the Yongding River estuary and the Tianjin Harbor, China, during 24–26 July 2007, and analyzed for 7Be and 210Pb activities. Due to localized hydrodynamic patterns and frequent disturbance from dredging activities, steady-state sedimentation features were not observed in this study. As demonstrated in the 7Be and 210Pb profiles, the temporal and spatial variations of these radionuclides support a non-steady state depositional environment in the study area. By comparing 7Be and 210Pb inventories in the sediments with those of the atmospheric source, we found that: 1) sediments dredged from the Tianjin Harbor or eroded from nearby estuarine and coastal areas are retained in the western Bohai Bay for relatively short intervals (several months), as reflected in the relatively high 7Be inventories in the western Bohai Bay; 2) over the long-term (years to decades), 210Pb inventories in the sediments imply that there is a net on-shore transport of sediments, and the sediments are mass-balanced in the entire study area. Overall, our results suggest that the sediments are retained in the estuaries and the western Bohai Bay despite local variability in sediment dynamics and disturbance due to human activities.     

Modeling transportation of suspended solids in Zhujiang River estuary, South China

A three-dimensional transportation model for suspended solids （SS） in Zhujiang （Pearl） River estuary, South China, was developed by coupling with a three-dimensional hydrodynamic model. The model was validated using hourly measured data of sediment contents during 25-26, July 1999. The results showed that modeled contents matched well with measured ones and that the modeled top layer distribution agreed with the remotely sensed image of suspended solids in summer. The modeled results showed clearly the layers of suspended solids in depth, with larger sediment contents in lower layers though in the interface between salt water and freshwater the lowest contents appeared in middle layer. In overall, the suspended solids inflow from 8 rivers,transport southwestward, and carried by strong coastal flow in Zhujiang River estuary. Contours of sediment contents in the estuary spread further to the open sea during ebb tide rather than flood tide which reflects that the suspended solids in the estuary are land sourced.     

PHYSICAL AND INTERFACIAL CHEMISTRY OF HUANGHE ESTUARY

Summarized results of studies on the physical and interfacial chemistry of the Huanghe estuary are presented as follows: 1. The relationship between the exchange ratio (%) and pH for the Cu (II)-Sedi.ments of the Huanghe Estuary and that of the Cu (II)-illite system were observed to be very similar. 2. A stepwise ion/coordination particle exchange isotherm of trace metal in Huanghe estuary sediment was derived. 3. The ion/coordination particle exchange between trace metal and Huanghe Estuary sediment is analogous to the interfacial chemical characteristic of illite.     

TraceeElements in Leccinum scabrum mushrooms and topsoils from Kłodzka Dale in Sudety Mountains, Poland

In the current study, we determined concentrations and transfer rates of Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, P, Rb, Sr and Zn to Brown Birch Scaber Stalks (Leccinum scabrum) mushrooms emerged in the area of Sudety Mountains (Sudetes) in Poland. Fruiting bodies and topsoil samples beneath L. scabrum were collected form the K odzka Dale. The trace elements were determined using validated method and inductively coupled plasma - atomic emission spectroscopy (ICP-AES) for final measurement. Mushrooms contained Ag, Cr, Hg, Co, Ni and Sr at < 1.0 μg/g dry weight; Ba and Pb at ~1.0 μg/g dw; Cd at < 5 μg/g dw; Cu and Mn at > 10 μg/g dw; Al and Ca at ~100 μg/g dw; Fe, Na, Rb and Zn at 100 to 500 μg/g dw, Mg at ~1,000 μg/g dw; P at ~5,000 μg/g dw and K at ~30,000 μg/g dw. Ca, Mn and Ni were nearly equally distributed between stipes and caps; stipes compared to caps were enriched in Ba, Na and Sr, while caps were enriched in Ag, Al, Cd, Co, Cr, Cu, Fe, K, P, Pb, Rb and Zn. The values of bioconcentration factor (BCF) varied highly depending on chemical element and were >1 for Ag, Cd, Cu, K, Mg, Na, P, Rb and Zn, while <1 for Al, Ba, Ca, Co, Cr, Fe, Mn, Ni, Pb and Sr. Topsoil showed elevated content of lead and mean concentration was 99 ± 32 μg/g dw, while cadmium was at 0.41 ± 0.15 and those two highly toxic to human elements occurred in edible caps of L. scabrum at 4.5 ± 2.2 and 2.9 ± 2.0 μg/g dw, respectively.     

GEOCHEMICAL STUDY OF THE CORE S01 IN THE SOUTH CHINA SEA

Si, Ti, Al, Fe, Mn, Ca, Mg, K, Na, P and Sr, Ba, Rb, Ga, V, Zr, Cr, Ni, Co, Cu, Zn, Pb,Nb, Y, Th, La in the core S01 were analyzed and the pattems of their enrichment are discussed.Enrichment of Na, Fe, Mn, Ba, Cu elements in the core indicates volcanic material are an importantsoarce of the sediments in the area. The enrichment frequently varying with the deposition processshows bottom volcanism is frequent in the area and that the studied area is a margin basin with distinctoceanic characteristics. The abnormal enrichment of Mn at the layers(0-15 cm and 665-670 cm) of the core could beclosely related to and so, indicate, the wide deposition hiatus that have occurred in the West PacificOcean and adjacent margin seas since Late Pleistocene.     

The estuarine chemistry of the Zhujiang River

Nine chemical species of Zn, Cd, Pb and Cu in the Zhujiang River estuary were measured by using the technique of ion-exchange, ultraviolet irradiation and anodic stripping voltammetry. According to the distribution of the nine species in percentage an estuarine chemical pattern of the metal elements Zn, Cd, Pb and Cu in the Zhujiang River estuary was roughly made, and its is suggested that this estuary has relatively great self purifying ability in respect to heavy metal pollution. This paper was published in Chinese in theOceanologia et limnologia sinica 13(1): 19–25, 1983.     

Potential Effects of Episodic Deposition on Nutrients and Heavy Metals in Decomposing Litters of Suaeda glauca in Salt Marsh of the Yellow River Estuary,China

Episodic deposition has been recognized as a major factor affecting the decomposition rate of detrital material in salt marshes. In this paper, three one-off burial treatments, no burial treatment(0 cm, NBT), current burial treatment(10 cm, CBT) and strong burial treatment(20 cm, SBT), were designed in intertidal zone of the Yellow River Estuary to determine the potential influences of episodic deposition on nutrient(C, N) and heavy metal(Pb, Cr, Cu, Zn, Ni, Mn, Cd, V and Co) variations in decomposing litters of Suaeda glauca. Results showed that although various burial treatments showed no statistical difference in decomposition rate of S. glauca, the values generally followed the sequence of CBT(0.002 403/d) SBT(0.002 195/d) NBT(0.002 060/d). The nutrients and heavy metals in decomposing litters of the three burial treatments exhibited different variations except for N, Cu, Cr, Ni and Co. Except for Mn, no significant differences in C, N, Pb, Cr, Cu, Zn, Ni, V and Co concentrations occurred among the three treatments(P 0.05). With increasing burial depth, Cr and Cd levels generally increased while Cu, Ni and Mn concentrations decreased. Although episodic deposition was generally favorable for C and N release from S. glauca, its influence on release was insignificant. In the three burial treatments, Pb, Cr, Zn, Ni, Mn, V and Co stocks in S. glauca generally evidenced the export of metals from litter to environment, and, with increasing burial depth, the export amounts increased greatly. The S. glauca were particular efficient in binding Cd and releasing Pb, Cr, Zn, Ni, Mn, V and Co, and, with increasing burial depth, stocks of Cu in decomposing litters generally shifted from release to accumulation. The experiment indicated that the potential eco-toxic risk of Pb, Cr, Zn, Ni, Mn, V and Co exposure would be serious as the strong burial episodes occurred in S. glauca marsh.     

Influences of hydrological regime on heavy metal and saltion concentrations in intertidal sediment from Chongming Dongtan,Changjiang River estuary,China

The tidal flat along the Changjiang(Yangtze) River estuary has long been reclaimed for the agricultural purposes, with the prevailing hydrological conditions during such pedogenic transformations being of great importance to their successful development. In this study, samples of surface sediment from Chongming Dongtan, situated at the mouth of the Changjiang River estuary, were collected and analyzed in order to understand how hydrological management can influence the concentrations of heavy metals and salt ions in pore water, and chemical fractionation of heavy metals during the reclamation process. We performed a series of experiments that simulated three dif ferent hydrological regimes: permanent flooding(R1), alternative five-day periods of wetting and drying(R2), continuous field capacity(R3). Our results exhibited good Pearson correlations coefficients between heavy metals and salt ions in the pore water for both R1 and R2. In particular, the concentrations of salt ions in the pore water decreased in all three regimes, but showed the biggest decline in R2. With this R2 experiment, the periodic concentration patterns in the pore water varied for Fe and Mn, but not for Cr, Cu, Pb and Zn. Neither the fractionation of Ni nor the residual fractions of any metals changed significantly in any regime. In R1, the reducible fractions of heavy metals(Cr, Cu, Zn and Pb) in the sediment decreased, while the acid extractable fractions increased. In R2, the acid extractable and the reducible fractions of Cr, Cu, Zn and Pb both decreased, as did the oxidizable fraction of Cu. These data suggest that an alternating hydrological regime can reduce both salinity and the availability of heavy metals in sediments.     

The distribution and variation of elements in sediments off the Huanghe (Yellow) River mouth

Surface sediment samples collected off the Huanghe (Yellow) River mouth during the period 2007–2009 were analyzed for major and trace element concentrations. Concentrations of 16 elements were measured using X-ray fluorescence spectrometry. Results demonstrate that sediment grain size is the dominant factor controlling the spatial variations of elemental concentrations. Correlation and cluster analyses allowed classification of the study area into four geochemical regions: Regions I and III are characterized by high concentrations of Al₂O₃, Fe₂O₃, MgO, Na₂O, K₂O, Cr, Cu, Mn, Ni, Pb, V, and Zn, and contain fine-grained sediments with mean grain size (M _z)<22 μm; and; Regions II and IV contain mostly coarse-grained sediments, and are characterized by high concentrations of SiO₂, Na₂O, and Zr. The sediment entering the sea from the Huanghe River and its tributaries is enriched in Ca. Thus, the Ca/Al ratio was used as an indicator of the proportion of sediments in the study area that originated from the Huanghe River. Ca/Al ratios decrease from Regions I and II (located in the nearshore zone of the Huanghe River delta) to Regions III and IV (distributed in the offshore zone of the northern Huanghe River delta, southern and southeastern Laizhou Bay area).     

Multielement analysis of deep-sea sediments by inductively coupled plasma mass spectrometry

Marine sediments were dissolved by HNO3-HF-HCIO4 in a sealed container at low pressure; I-IF was evaporated in an open container and salts were dissolved in HCl by heating, then transferred to 2% HNO3 solution. A total of 45 elements, including Li, Be, So, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, TI, Pb, Bi, Th and U, were measured by inductively coupled plasma mass spectrometry (ICP-MS). Condi-tions and sample experiments showed that this procedure defines a good experimental method which has the advantages of clear interference, easy operation and reliable results. The concentrations of the 45 elements could be used for resource exploration, envi-ronmental assessment and academic research.     

A study on element-stratigraphy of Okinawa Trough

Regular distribution patterns of elements Ca, Sr, K, Na, Mg, Fe, Mn, Ti, Cu, Co, Ni, Zn, Pb, Cr, Rb, Ba, Cd, and U in Late Quaternary strata have been studied in detail. The regional variation patterns of elements in these strata are similar to those in recent surface sediments, showing that the sedimentary environment has been relatively stable since Late Quaternary. Element distribution changes with the variations of lithological characters. Contents of Ca and Sr increase in coarse sediments, while those of other elements decrease. Na content increases in the pumice layer. Mn, content tends to increase sharply towards the surface layer. Ca content decreases sharply in strata where water depth is more than 2,000 m. The strata can be divided based on the distribution curves of element assemblages. The variations in contents of most elements in Holocene Series are smaller than those in Late Pleistocene Series, which might be related to the factors of glacial and interglacial changes, sea level fluctuations and material source differences. Contribution No. 1488 from Institute of Oceanology, Academia Sinica     

Mineral constituents in common chanterelles and soils collected from a high mountain and lowland sites in Poland

This paper reported the results of the determination of Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn in Common Chanterelles (Cantharellus cibarius) Fr. and surface soil layer (0-10 cm) underneath the fruiting bodies. Mushrooms and soils were collected from a lowland site in the Hel Peninsula (Baltic Sea coast) and a high mountain site in the Tatra Mountains. The trace elements were determined using validated method and inductively coupled plasma - atomic emission spectroscopy (ICP-AES). Common Chanterelles that emerged at sites poor in mineral nutrients podzols of the Hel Peninsula forests efficiently bioconcentrated several essential trace elements (K, P, Co, Cu, Mn, Na, Zn), while the abundance of those elements in carpophores was around half less compared to specimens from Zakopane region and which emerged in soils much richer in minerals. Common Chanterelles collected at two spatially distant background areas in Poland were only weakly contaminated with metals such as Ag, Cd, Hg and Pb. The maximum tolerable Cd and Pb contents of certain cultivated mushrooms are regulated in the European Union by law and these hazardous metals in C. cibarius were far below tolerance limits set.