Impact of trace metals on denitrification in estuarine sediments of the Douro River estuary,Portugal

Denitrification influences the nitrogen budget in estuaries by removing fixed nitrogen from the inorganic pool; rates are dependent on both geological and geographic conditions as well as increasing anthropogenic impacts. In this study the effects of copper (Cu), chromium (Cr), zinc (Zn), cadmium (Cd) and lead (Pb), on the denitrification pathway were evaluated in subtidal and intertidal sediments of the Douro River estuary. Dinitrogen, N₂O and NO₂⁻ production rates were measured in triplicate slurries of field samples under different treatments of metal concentrations. Results demonstrated that similar metal amendments led to different site responses for denitrification, suggesting that variations in sediment properties (metal concentrations, grain size, organic matter content, etc.) and/or differences in denitrifying community tolerance modulate the level of metal toxicity. Denitrifying communities in subtidal muddy sediments were not affected by increasing concentrations of metals. In contrast, intertidal sandy sites revealed high sensitivity to almost all trace metals tested; almost complete inhibition by Cr (95%) and Cu (85%) was observed for 98 and 79 μg per gram of wet sediment respectively, and by Zn (92%) at the highest concentration added (490 μg per gram of wet sediment). Moreover, the addition of trace metals stimulated N₂O and NO₂⁻ accumulation in intertidal sandy (Zn, Cu, Cr and Cd) and muddy sediments (Cu and Zn), demonstrating a pronounced inhibitory effect on specific steps within the denitrification enzymatic system. In summary, the results obtained suggest that, according to the type of estuarine sediment, trace metals cannot only reduce total N removal from an estuary via denitrification but also can enhance the release of N₂O, a powerful greenhouse gas.     

Community Metabolism in Microbial Mats: The Occurrence of Biologically-mediated Iron and Manganese Reduction

Community metabolism and nutrient, iron (Fe) and manganese (Mn) cycling were examined in two intertidal, marine, microbial mat communities during short (4–5 days) incubations in closed, flow-through microcosms. Sediment microcosms were incubated under either light (light–dark cycles) or dark (continuous darkness) conditions to assess the effect(s) of photosynthetic oxygen production and microalgal activity on nutrient, Fe and Mn cycling. The effects of chemical redox reactions between reduced sulphur (S), Fe and Mn cycling were examined by blocking sulphate reduction, and reduced S production, with 25 mM molybdate while incubating under dark conditions.In light-incubated microcosms, negligible fluxes of nutrients (nitrogen and phosphorus) and trace metals were observed. A substantial sediment–water flux of reduced Fe (Fe²⁺) and Mn (Mn²⁺) was observed in microcosms incubated under continuous darkness; highest fluxes were observed in molybdate-amended microcosms. At both sites, biologically-mediated redox reactions accounted for a substantial (>50%) portion of the Fe²⁺and Mn²⁺flux. Both microbial mat communities exhibited similar rates of gross photosynthetic oxygen (O₂) production, but dramatically different rates of net benthic O₂flux. Distinct patterns of net O₂production and trace metal cycling arose from differences in either trace metal oxide availability or reactivity (mineralogy), organic carbon mineralization rates, or sediment characteristics (porosity). Variations in the microbial community responsible for trace metal cycling could have also contributed to the pattern. The present data illustrate that chemically-mediated redox reactions between metal oxides and reduced S complicate interpretation of Fe and Mn fluxes, underscoring the need to separate chemical and biological reactions when attempting to determine the role of biological trace metal reduction in organic carbon oxidation.     

Trace metal-binding proteins in marine molluscs and crustaceans

Some marine invertebrates, such as the American oyster, Crassostrea virginica, the blue crab, callinectes sapidus and the American lobster, Homarusamericanus, concentrate trace metals in their tissues. The occurrence of metallothionein, a low molecular weight, sulfur-containing metal-binding protein, has been correlated with elevated levels of trace metals in these organisms. It is our hypothesis that, whilst metallothioneins are involved in the sequestration of elevated levels of trace metals, they primarily function in regulating normal metal metabolism. In this paper we describe recent field and laboratory experiments designed to examine how oysters, blue crabs and lobsters manage accumulated cadmium, copper and zinc. The possible rôles of metallothionein, as well as the tissue distribution of metals, are emphasized. Metallothioneins were found in all animals we examined; concentrations of metallothioneins and the the amount of bound trace metals are related to time of exposure. We have also demonstrated that the laboratory developed metallothionein models for blue crabs and lobsters may be useful in predicting the partitioning of trace metals in animals living in environments polluted with trace metals.     

Trace metals (Cd, Cr, Cu, Fe, Ni, Pb, and Zn) in feathers of Black-browed Albatross Thalassarche melanophrys attending the Patagonian Shelf

We investigated the concentrations of cadmium, chromium, copper, iron, nickel, lead and zinc among feather tissues in sexes of Black-browed Albatross Thalassarche melanophrys killed in longliners off Argentina in 2005. We found no different metal concentration with sex for cadmium, copper, iron, lead and zinc in feathers of adult birds, though there were significant body-size differences between sexes. However, the concentrations of trace metals differed significantly among the type of feather within individual bird. The mean concentrations of copper, iron, and zinc in breast feathers of T.?melanophrys were lower than those reported for the species from Georgias del Sur/South Georgia, the southern Indian Ocean and for other seabirds' worldwide. While cadmium fall within the known range of concentrations for bird feathers lead were not. Our results may be indicating that level of pollution in Patagonia may not be as negligible as previously thought at least for some trace metals.     

Barnacles as biomonitors of trace metal availabilities in Hong Kong coastal waters: changes in space and time

The use of selected organisms as biomonitors of trace metal bioavailabilities allows comparisons to be made over space and time. The concentrations of 11 trace metals (arsenic, cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel, silver, zinc) were measured in the bodies of two barnacle species, Balanus amphitrite and Tetraclita squamosa, from up to 18 littoral sites from Hong Kong coastal waters in April 1998. These data provide evidence on the geographical variation in metal bioavailabilities at this time, and are compared selectively against historical data sets for 1986 and 1989. Geographical variation in bioavailabilities is clear for several metals, with hotspots for arsenic, copper, nickel and silver at Chai Wan Kok, and for lead in Junk Bay. Victoria Harbour sites head the rankings for silver and arsenic, and Tolo Harbour sites exhibit relatively elevated cobalt, manganese and zinc. Many bioavailabilities of trace metals to barnacles are lower in Hong Kong coastal waters in 1998 than in 1986. The two barnacle species are widespread and the extensive data set presented is a benchmark which can be compared to the results of similar biomonitoring programmes elsewhere in the Indo-Pacific and beyond.     

Spatial and seasonal variations in depth profile of trace metals in saltmarsh sediments from Sapelo Island, Georgia, USA

This study was undertaken to elucidate the impact of early diagenetic processes on the accumulation of trace metals in Sapelo Island saltmarsh sediments as a function of time, space and sediment properties. Samples were collected from three sites in summer (May 1997) and winter (January 1998) along a transect from an unvegetated Creek Bank through a vegetated Tidal Levee to the vegetated midmarsh with evident lateral heterogeneity caused by hydrologic regime, macrophytes and microbial and macrofaunal activities. A suite of trace metals (As, Ba, Cr, Co, Cu, Cd, Mo, Ni, Pb, Th, Ti, U, V, Zn and Zr) was analyzed to obtain their depth-distribution at the three sites. Spatially marked differences were observed, that were primarily related to hydraulic flushing of trace metals away from the sites in high-energy regimes, rapid downward mixing and reworking of sediment via bioturbation, and below-ground degradation and production of Spartina biomass. Although sulfate reduction and the formation of acid volatile sulfide and pyrite were dominant processes throughout the marsh, the trace metal scavenging role of sulfides was not apparent. However, possible sulfurization of organic matter, leading to enhanced trapping of trace metals with organic carbon, may have played an important role in sequestration of trace metals.No similarity was observed visually between the depth trends of trace metals and sediment properties (grain size, iron-oxyhydroxide content, acid volatile sulfides and pyrite content) that are known to play a major role in trace metal partitioning. Only organic carbon content closely followed the trace metal profiles at all the three sites. Minor variation in depth-integrated sediment trace metal content was observed seasonally at each of the three sites. Furthermore, the depth trend of profiles of individual trace metals also did not vary significantly over the seasons either.     

An investigation of the suitability of amberlite XAD-1 resin for studying trace metal speciation in seawater

Amberlite XAD-1 resin was examined to test its suitability for extracting organic complexes of copper, zinc and iron from seawater. At low flow rates and at loading capacities far below theoretical values, the adsorption of these metals is not reproducible and the results are reminiscent of the behaviour observed when the adsorption capacity is being exceeded or flow rates are too high. It is suggested that the resin also adsorbs small but significant amounts of inorganic ions from seawater and that this effect makes the resin unsuitable for quantitative measurements of trace metal speciation.     

Mechanism Study of Transport and Distributions of Trace Metals in the Bohai Bay,China

This study shows that there are two regions with high trace metal concentrations in the Bohai Bay, China. The numerical hydrodynamic model coupled with geochemical analysis was applied to understand the mass transport and sedimentation in the bay. The modeling results show that the two regions are located within the residual current vortexes. Results from the particle-tracking model indicate that the trace metals released from the land sources enter the regions and take a relatively long residence time in the vortexes. The sediment radionuclide data indicates that the two regions experienced continuous and high sedimentation, and trace metals are prone to deposit in the regions. The correlations among trace metals, residual currents and radionuclides data suggest that the tides are the governing factor controlling the distributions of the trace metals in the bay. The consistence among these results also supports the reliabilities of the numerical simulation results of water and trace metal transport in this study.     

Coastal Pollution Mitigation with Lime and Zero Valent Iron

The Taiwan Strait region has many miles of coastline, and the Taiwan Straits Tunnel (TST) project faces many potential pollution problems as construction proceeds through sensitive areas. Conventional approaches for pollution mitigation require further examination. The recent development of nanoscale particle technology has shown distinct advantages for contaminant attenuation and ground improvement. This paper is focused on trace metals and is part of the overall effort to develop the nanoscale particle technology. Trace metals in ground and surface waters represent a continued threat to human and ecological health. One of the difficulties in removing toxic concentrations of trace metals from solution is the variable oxidation state and amphoteric nature of multiple constituents. In particular, while cationic metals (e.g., Pb²⁺, Cd²⁺, Ni²⁺) may be rendered less mobile under high pH conditions, anionic metals (e.g., AsO₄^3-, CrO₄^2-, SeO₄^2-)may become more mobile. The objective of this research was to evaluate the sorption of both cationic and anionic trace elements, including arsenic (As), cadmium (Cd), chromium (Cr) and selenium (Se) under batch conditions. Mixtures of a local residual soil were tested alone and in combination with lime and zero valent iron. It was hypothesized that lime would raise the pH and precipitate positively charged metals while zero valent iron would create reducing conditions favorable to the immobilization of negatively charged metals. Results indicate that the use of lime and/or zero valent iron can increase the sorption capacity of soil. Compared to the baseline soil, sorption capacity increased with addition of lime for arsenic and cadmium while it decreased for chromium and selenium. In the case of zero valent iron addition, sorption capacity increased for cadmium, chromium and selenium, while showing no change for arsenic. When both lime and zero valent iron were used, the sorption capacity increased for all metals tested. These results suggest that the combined use of lime and zero valent iron may serve as an alternative treatment technology for removing trace metals from contaminated water systems.     

珠江河口微量金属的相态变化与生物效应

通过实验，研究了珠江河口海区悬浮颗粒物质对微量金属Ｃｕ，Ｚｎ和Ｃｄ化学相态和生物毒性的影响，以及腐植酸对微量金属Ｃｕ，Ｚｎ和Ｃｄ络合作用和生物毒性的影响，从而回答一些目前仍有争议的问题。     

Eelgrass (Zostera marina L.) as an indicator organism of trace metals in the Limfjord,Denmark

The concentrations of Pb, Cu, Cd and Zn were determined in above- and belowground parts of eelgrass (Zostera marina L.) at forty stations in a shallow, brackish water area (the Limfjord, Denmark). The concentrations of the trace metals were significantly elevated near the cities of Aalborg (Pb, Cu) and Struer (Cd). Trace metal concentrations in above and belowground parts of eelgrass were log-normal distributed and the concentrations of Cd, Cu and Zn in aboveground parts were significantly higher than in belowground parts. Furthermore, a significant correlation between trace metal concentrations in above- and belowground parts was found. The background level of trace metal concentrations in eelgrass in the Limfjord was estimated.The application of eelgrass as a monitoring organism is discussed; it is suggested that the concentration of some trace metals in above- and belowground parts of eelgrass may be used as a measure of the bioavailable fraction of these trace metals in ambient and interstitial water (sediment), respectively.     

Coastal Pollution Mitigation with Lime and Zero Valent Iron

The Taiwan Strait region has many miles of coastline, and the Taiwan Straits Tunnel (TST) project faces many potential pollution problems as construction proceeds through sensitive areas. Conventional approaches for pollution mitigation require further examination. The recent development of nanoscale particle technology has shown distinct advantages for contaminant attenuation and ground improvement. This paper is focused on trace metals and is part of the overall effort to develop the nanoscale particle technology. Trace metals in ground and surface waters represent a continued threat to human and ecological health. One of the difficulties in removing toxic concentrations of trace metals from solution is the variable oxidation state and amphoteric nature of multiple constituents. In particular, while cationic metals (e.g., Pb²⁺, Cd²⁺, Ni²⁺) may be rendered less mobile under high pH conditions, anionic metals (e.g., AsO₄ ^3?, CrO₄ ^2?, SeO₄ ^2?)may become more mobile. The objective of this research was to evaluate the sorption of both cationic and anionic trace elements, including arsenic (As), cadmium (Cd), chromium (Cr) and selenium (Se) under batch conditions. Mixtures of a local residual soil were tested alone and in combination with lime and zero valent iron. It was hypothesized that lime would raise the pH and precipitate positively charged metals while zero valent iron would create reducing conditions favorable to the immobilization of negatively charged metals. Results indicate that the use of lime and/or zero valent iron can increase the sorption capacity of soil. Compared to the baseline soil, sorption capacity increased with addition of lime for arsenic and cadmium while it decreased for chromium and selenium. In the case of zero valent iron addition, sorption capacity increased for cadmium, chromium and selenium, while showing no change for arsenic. When both lime and zero valent iron were used, the sorption capacity increased for all metals tested. These results suggest that the combined use of lime and zero valent iron may serve as an alternative treatment technology for removing trace metals from contaminated water systems.     

四种重金属对海洋钙质角毛藻的毒性

研究了Ｈｇ＾２＋、Ｃｕ＾２＋、Ｚｎ＾２＋、Ｃｄ＾２＋４种重金属,其单一及４种混合对海洋单胞藻钙质角毛藻Ｃｈａｅｔｏｃｅｒｏｓ ｃａｌｃｕｔｒａｎｓ的毒性效应,结果表明：单一的重金属毒性强于４种重金属混合,而且不同重金属对单胞藻的毒性效应有所不同,其毒性均Ｈｇ＾２＋〉Ｃｕ＾２＋〉Ｚｎ＾２＋〉Ｃｄ＾２＋。     

胶州湾水生系统中Pb、Zn 的分布特征及其在生物体中的浓缩

利用在胶州湾采集的47组同站位多介质样品,进行了痕量金属Pb、Zn及其它环境因子的化学成分测试,讨论了胶州湾水-沉积物-生物系统中Pb、Zn的生物地球化学总体特征及其在各介质平面上的分布,揭示了胶州湾水-沉积物-生物系统对陆源物质输入的响应.垂向上表层沉积物是Pb、Zn组分的富集带,该系统中的生物相对于其所处水环境具有显著的富集作用,生物体中Pb、Zn生物浓缩系数分别为36、935;横向上,Pb、Zn在底层水和沉积物介质中的分布主要受控于河口,即高值区分布于胶州湾的各个主要河口区,特别是在沉积物中金属组分浓度的高值区主要集中分布于胶州湾的东部.而孔隙水中Pb、Zn的高值主要分布于水交替较弱的海域,如红岛前缘.但生物体中的痕量金属组分化学场空间分布规律与上述各介质的化学场均不吻合,亦即是生物体中痕量金属组分的浓度与其所处环境中的同名金属组分浓度无关.作者认为,生物对痕量金属组分的富集并不简单地取决于它所处环境介质中同名金属组分的总量,而存在形态上的选择性.通过回归分析揭示了孔隙水对生物体中Pb、Zn的富集贡献较大.     

Assessment of coastal marine pollution in Galicia (NW Iberian Peninsula); metal concentrations in seawater,sediments and mussels (Mytilus galloprovincialis) versus embryo-larval bioassays using Paracentrotus lividus and Ciona intestinalis

Sediments from three Galician Rias were tested for toxicity using sea-urchin and ascidian sediment elutriate embryo-larval bioassays. Trace metal contents in seawater, sediments and mussels were also determined and subjected to multidimensional scaling methods which grouped stations according to chemical contamination. High metal contents were found in seawater, sediments and mussels from the Ria of Pontevedra, and moderate levels were detected in the Ria of Vigo and Ria of Arousa. The results revealed that samples assessed as toxic, according to the sea-urchin and ascidian embryo-larval bioassays, were among the most polluted by trace metals. A good agreement was reported between ordination plots resulting from applying multidimensional scaling to the chemical data, and the results of the biological endpoints tested.     

Precipitation of heavy metals in produced water: influence on contaminant transport and toxicity

Produced water undergoes changes in its physical chemistry including precipitation of heavy metals after being discharged and mixed with ambient seawater. Potential impacts of the precipitation of heavy metals on their transport and toxicity were studied using samples from offshore oil production sites on the Scotian Shelf off eastern Canada. Concentrations of aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel and zinc were measured in total, particulate and dissolved fractions together with Microtox tests for assessment of toxicity. Heavy metals in produced water were transformed from dissolved to particulate phase in a period of hours under oxygenated conditions, and aggregated to larger particles that settle rapidly (>100 m/day) over a few days. In addition, there was production of buoyant particles comprised of heavy metal precipitates sequestered onto oil droplets that were transported to the surface. The particulate fraction was generally more toxic than the dissolved fraction. This was evident at the mixing interface between produced water and seawater where elevated particulate and toxicity levels were observed. Laboratory studies suggest an increase in the toxicity of discharged produced water over time. Time-series experiments showed a sustained toxic response for more than a week following the oxidation of freshly discharged produced water that initially elicited little or no toxic response in the Microtox test. Chemical processes identified in this study, namely precipitation of heavy metals and consequent settling and rising fluxes of particles, will influence the toxicity, the fate and the transport of potential contaminants in the produced water. Therefore, these processes need to be considered in assessment of the environmental impact associated with offshore oil and gas operations.     

Uptake and distribution of N, P and heavy metals in three dominant salt marsh macrophytes from Yangtze River estuary, China

We examined the variation in aboveground biomass accumulation and tissue concentrations of nitrogen (N), phosphorus (P), copper (Cu), zinc (Zn) and lead (Pb) in Phragmites australis (common reed), Spartina alterniflora (salt cordgrass), and Scirpus mariqueter throughout the growing season (April-October 2005), in order to determine the differences in net element accumulation and distribution between the three salt marsh macrophytes in the Yangtze River estuary, China. The aboveground biomass was significantly greater in the plots of S. alterniflora than in the plots of P. australis and S. mariqueter throughout the growing season (P<0.05). In August, the peak aboveground biomass was 1246+/-89 gDW/m(2), 2759+/-250 gDW/m(2) and 548+/-54 gDW/m(2) for P. australis, S. alterniflora and S. mariqueter, respectively. The concentrations of nutrients and heavy metals in plant tissues showed similar seasonal patterns. There was a steady decline in element concentrations of the aboveground tissues from April to October. Relative element concentrations in aboveground tissues were at a peak during the spring sampling intervals with minimum levels during the fall. But the concentrations of total nitrogen and total phosphorus in the belowground tissues were relatively constant throughout growing season. Generally, trace metal concentrations in the aboveground tissues of S. mariqueter was the highest throughout the growing season, and the metal concentrations of S. alterniflora tissues (aboveground and belowground) were greater than those of P. australis. Furthermore, the aboveground pools of nutrients and metals were consistently greater for S. alterniflora than for P. australis and S. mariqueter, which suggested that the rapid replacement of native P. australis and S. mariqueter with invasive S. alterniflora would significantly improve the magnitude of nutrient cycling and bioavailability of trace metals in the salt marsh and maybe transport more toxic metals into the water column and the detrital food web in the estuary.     

Toxic chemistry of heavy metals on Isochrysis galbana (parke)in inshore water

Effects of heavy metals on Isochrysis galbana (Parke) were studied in our laboratory. The research focused on toxic effects of metals on algal cells, effects of water-soluble and lipid-soluble organic ligands on metal toxicity and processes of metal uptake by cells. Interactions between two metals and the mechanisms involved were also studied in detail. Finally, some relationships between toxicity and chemical property of metals were revealed.     

北太平洋大气沉降的时空特征及其对副极区海洋生态系统的影响

北太平洋副极地海区作为全球海洋三个高营养盐低叶绿素(high nutrient and low chlorophyll, HNLC)海区之一, 其浮游植物生长受到微量元素铁的限制。对于开阔大洋, 大气沉降是海洋表层铁的一个重要来源, 铁元素沉降进入海洋后能够促进浮游植物生长, 进而引起海洋初级生产力和生物泵的响应。本文利用SPRINTARS(Spectral Radiation-Transport Model for Aerosol Species)模式的时长为20a的日均大气沉降数据, 对北太平洋海区大气沉降的时空特征进行了分析。结果表明, 进入北太平洋海区的大气沉降量为26.81Tg·a^-1, 并且存在显著的季节变化: 春季最高, 冬季最低, 5月份进入海洋的沉降量达到峰值。大气沉降主要来源于陆地区域, 在风场的驱动下向海洋传输, 因此大气沉降量的空间分布呈现出西高东低的特征。本文以2010年8月中旬卫星观测到的一次强沙尘(即高大气沉降量)事件为例, 研究了大气沙尘的传播路径。进一步结合2001年4月9—12日及2008年4月20—22日的沙尘事件, 分析了西北太平洋K2站位(47°N, 160°E)附近海域海洋初级生产力对大气沉降——沙尘事件的响应。结果表明, 三次沙尘事件后, K2站位的颗粒有机碳通量、叶绿素浓度均有明显增加, 即沙尘事件对北太平洋副极区海洋初级生产力存在促进作用。     

Requirement of endogenous iron for cytotoxicity caused by hydrogen peroxide in Euglena gracilis

It is widely thought that redox-active metals in cells such as iron or copper catalyze the reduction of hydrogen peroxide to toxic hydroxyl radicals or their equivalent. However, this has not been directly demonstrated in vivo. To probe this requirement, the freshwater microorganism Euglena gracilis was used. Its intracellular iron content can be modulated by the concentration of iron in the defined growth medium without effect on the proliferation rate of the cells. E. gracilis contains two large storage pools of cytosolic iron which can be monitored to assess cellular iron status. The toxicity of H₂O₂ in E. gracilis was inversely related to the amount of iron in the extracellular medium. At high levels of external iron, the metal carried out the Fenton reaction with H₂O₂ outside the cell, producing hydroxyl radicals as detected by electron-spin resonance spin-trapping experiments. This reaction reduced the amount of H₂O₂ that could diffuse into cells to cause toxicity. When cells with different intracellular iron content were placed in iron-deficient media, the the toxicity of H₂O₂, measured by inhibition of proliferation, was directly related to the concentration of internal iron. Using cells deficient in iron, this oxidant did not inhibit proliferation at low concentration but was somewhat effective at higher concentrations. Although the iron chelating agents, 1,10-phenanthroline and desferrioxamine, also depressed cytosolic iron, they were cytotoxic to E. gracilis and so could not be used unambiguously to examine the role of intracellular iron in the toxic effects of hydrogen peroxide.