Distribution and assessment of sediment toxicity in Tamaki Estuary,Auckland, New Zealand

Heavy metal levels in surface sediments from Tamaki Estuary demonstrate significant up estuary increases in Cu, Pb, Zn, Cd and mud concentrations. Increased metal levels towards the head of the estuary are linked to local catchment sources reflecting the historical development, industrialisation and urbanisation of catchment areas surrounding the upper estuary. The relatively narrow constriction in the middle estuary (Panmure area), makes it susceptible to accumulation of upper estuary pollutants, since the constriction reduces circulation and extends the time required for fine waterborne sediments in the upper estuary to exchange with fresh coastal water. As a result fine fraction sediments trapped in the upper estuary facilitate capture and retention of pollutants at the head of the estuary. The increase in sandy mud poor sediments towards the mouth of the estuary is associated with generally low metal concentrations. The estuary’s geomorphic shape with a mid estuary constriction, sediment texture and mineralogy and catchment history are significant factors in understanding the overall spatial distribution of contaminants in the estuary. Bulk concentration values for Cu, Pb, Zn, and Cd in all the studied surface samples occur below ANZECC ISQG-H toxicity values. Cd and Cu concentrations are also below the ISQG-L toxicity levels for these elements. However, Pb and Zn concentrations do exceed the ISQG-L values in some of the surface bulk samples in the upper estuary proximal to long established sources of catchment pollution.     

Fluxes of organic carbon in Manukau Harbour, New Zealand

We collated information on the sources and sinks of organic carbon in Manukau Harbour, a shallow temperate estuary. Two contrasting inner harbor regions were considered; the northern region, which is urbanized and receives a major load of sewage wastewater, and the southern region, where allochthonous inputs are dominated by the runoff from small rural streams. Although high levels of dissolved nitrogen in the wastewater supported phytoplankton blooms in the northern region, total primary production there was similar to that in the southern region (ca. 300 g C m^?2yr^?1). By contrast, high concentrations of organic carbon in the wastewater resulted in an additional input to the northern region of 120 g C m^?2 yr^?1. Loads from runoff and streams to both regions were low. At 350 g C m^?2 yr^?1, total respiration in the northern region exceeded total production, so the region was slightly heterotrophic. Respiration was lower in the southern region (270 g C m^?2 yr^?1), which was net autotrophic. Some carbon was exported from each region to the outer harbour (50–80 g C m^?2 yr^?1). Dissolved oxygen levels in the northern region were somewhat depleted at times; and the high numbers of microzooplankton indicated consumption was enhanced there. Apart from a relatively small area of organic enrichment close to the wastewater discharge, benthic consumers in the harbor appeared to be limited by physical disturbance (by wind-waves) rather than by food availability. Improved wastewater treatment is expected to substantially reduce the allochthonous input to the northern region, with the total input of carbon in the future being only slightly higher than that to the southern region.     

Spatial variations in heavy metals on tidal flats in the Yangtze Estuary,China

Surface samples are used to determine onshore-offshore variations in heavy metal concentrations on tidal flats on Chongming and Hengsha Islands in the Yangtze Estuary, China. The Mann-Whitney U-Test suggests that proximity to the estuarine turbidity maximum does not result in significantly higher metal concentrations on tidal flats. Principal Components Analysis shows that grain-size is the primary control on metal concentrations, reflecting the occurrence of salt marsh and mud and sand flats. Sediment quality is comparable to that of pristine estuaries because of dilution by high river sediment loads.     

Accumulation of muds and metals in the Hudson River estuary turbidity maximum

 In the Hudson River estuary, fine mud and toxic metals are enriched in the upstream turbidity maximum. The mechanisms causing the enrichment were assessed through the analysis of suspended-sediment concentration (SSC) (bottom and surface), particle size, and trace metal distributions. Bottom SSCs varied across the study area by a factor of ten, and the turbidity maximum activity was observed in between kilometers 45 and 80. The particle-size analysis defined two accumulation modes: <4.65 and >22.1 μm. The ratio of the fine-to-coarse mode increased from 1.75 to 2.75 in the turbidity maximum. The fine mud concentration (55–60%) in the turbidity maximum was found to have a high correlation (r=0.98;p<0.005) with the concentration of <2-μm particles. A conceptual model was derived in order to understand the possible mechanisms by which fine mud (and specifically <2-μm particles) is concentrated. The two dominant size modes were analyzed for toxic metals. The upstream tributaries are major sources of metals compared to point sources at downstream locations. In the turbidity maximum, Cd, Cu, Zn, and Pb are significantly enriched compared to average shale metal values and ERM toxicity guidelines by 580, 42, 10, 16 and 12, 7, 2.4, 1.4 times, respectively. Decreasing metal concentrations downstream of the turbidity maximum imply that Haverstraw Bay acts as temporary storage for fine particles and enriched metals. It is demonstrated in this study that toxic metals are enriched in Haverstraw Bay due to the mud accumulation. The high levels of toxic metals in the sediments of the Hudson River estuary are a major concern because human activities (dredging and river traffic) cause resuspension of sediments and can change the mobility patterns of bioavailable contaminants. Received: 4 June 1997 · Accepted: 9 September 1997     

Heavy metal history from cores in Wellington Harbour,New Zealand

Analysis of ten heavy metals (Ag, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, Zn) in six sediment cores from Wellington Harbour show both anthropogenic enrichments and diagenetic modifications. Absolute concentrations determined by two methods, x-ray fluorescence and acid leaching for bioavailability, are not comparable. However, vertical trends in concentrations of the cored sediment are comparable. To assess levels of anthropogenic pollution, enrichment factors (enriched concentrations in upper core divided by background levels in lower core) are preferred over index of accumulation (I _geo) values because preindustrial or background levels of heavy metals are well constrained. The ten metals are placed into three groups: (1) Cu, Pb, and Zn, which show the most anthropogenic enrichment; (2) As, Cd, Cr, Ni, and Sb, which are often associated with anthropogenic pollution but show only minor enrichment; and (3) Fe and Mn, which are diagenetically enriched. Assuming harbor waters are well mixed, anthropogenic enrichments of Cu, Pb, and Zn, are time correlative, but the degree of enrichment depends on the method of analysis and core location. Levels of As, Cd, Pb, and Zn show small variations in preindustrial sediments that are not related to changes in grain size and probably result from changes in the oxidation-reduction potential of the sediments and salinity of the pore waters.     

Soil and groundwater pollution of an urban catchment by trace metals: case study of the Addis Ababa region, central Ethiopia

Analysis of the total heavy metal (Cr, Cd, Pb, As, Cu, Ni, Zn, Co) concentration was performed on 33 soil samples taken from different profiles and soil types in a highly urbanized and industrial sector of Addis Ababa, central Ethiopia. They were analyzed using aqua regia extraction coupled with a four-stage sequential extraction (SE) procedure. The objectives of the analysis were to investigate the degree of soil heavy metal contamination, its binding forms, mobility and the implications for the groundwater resource. The results show a relatively high content of the analyzed trace metals in the soil attributed to anthropogenic and geogenic sources. Although most of the trace metals are found in the upper few centimeters of the residual soils, because of churning processes within the black cotton soils, vertical distribution of the trace metals is complex. According to the heavy metal SE analysis, the major heavy metal contribution is from the residual followed by the hydroxide phases. Groundwater heavy metal contamination is present with more than 90 and 50% of the analyzed groundwater samples exceeding WHO guidelines for Cr and Cd, respectively. Since the degree of soil heavy metal contamination has apparently not surpassed the soil’s buffering capacity, it appears that the transport path of these toxic metals to the groundwater is through fractures, joints, and related preferential flow paths.     

Heavy metals on tidal flats in the Yangtze Estuary, China

 Five short cores were used to examine heavy metals on tidal flats in the Yangtze Estuary, China. Statistically insignificant trends in lead-210 and most metals with core depth are primarily due to high sedimentation rates. Metal contents are correlated with percent aluminum, which reflects the clay contents in the sediment, and they are also affected by proximity to sewage outlets and local industry. National standards for copper are exceeded in four cores, zinc in one core, and arsenic in all cores. Heavy metal contents are generally lower on the Yangtze tidal flats compared to most other estuaries because high sediment loads dilute metal inputs. Received: 1 June 1999 · Accepted: 15 August 2000     

Speciation and mobility of heavy metals in mud in coastal reclamation areas in Shenzhen,China

Coastal reclamation has been carried out along the coastal areas near Shenzhen, China in a large scale since 1980s by dumping fill materials over the marine mud at the sea bottom. Usually the area to be reclaimed is drained first and some of the mud is air-dried for a few weeks before it is buried by fill. After reclamation, the terrestrial groundwater, which is relatively acidic and with high dissolved oxygen, gradually displaces the seawater, which is alkaline with high salinity. The changes in the burial conditions of mud and the properties of the pore water in the mud may induce the release of some heavy metals into the mud. Field survey confirms that the pH and salinity of the groundwater in the reclamation site are much lower than the seawater. Chemical analyses of mud and groundwater samples collected from the reclamation sites reclaimed in different years indicate that most of the heavy metals in the mud decrease gradually with time, but the heavy metals in the groundwater are increased. The release of heavy metals into pore water due to reactivation of heavy metals in the mud is of environmental concern. To understand why some of the heavy metals can be released from the mud more easily than others, a sequential extraction method was used to study the operationally determined chemical forms of five heavy metals (Cu, Ni, Pb, Zn, and Cd) in the mud samples. Heavy metals can be presented in five chemical forms: exchangeable, carbonate, Fe–Mn oxide, organic, and residual. Ni and Pb were mainly associated with the Fe–Mn oxide fraction and carbonate fraction; Zn was mainly associated with organic fraction and Fe–Mn oxide fraction, while Cu and Cd were associated with organic fraction and carbonate fraction, respectively. If the residual fraction can be considered as an inert phase of the metal that cannot be mobilized, it is the other four forms of heavy metal that cause the noticeable changes in the concentration of heavy metals in the mud. On the basis of the speciation of heavy metals, the mobility of metals have the following order: Pb (36.63%) > Cu (31.11%) > Zn (20.49%) > Ni (18.37%) > Cd (13.46%). The measured metal mobility fits reasonably well with the degree of concentration reduction of the metals with time of burial observed in the reclamation site.     

A contemporary contamination record of stormdrain and harbour sediments, Wellington, New Zealand

 Sediments from stormdrain catchments and outlets in Wellington city and sediment traps from Wellington Harbour were sampled for trace metal content. Samples were analysed for total metal content using XRF and ICP-MS. High values of Pb and Zn were found in stormdrain catchments and outlets, decreasing to elevated background rock levels in the harbour. Maximum values were recorded in an inner city stormdrain catchment, with levels of Pb (4605 ppm), Cu (2981 ppm) and Zn (3572 ppm) all higher than the biological probable effects levels (PEL). Concentrations of As, Cr, Cu, Pb, Ni and Zn concentrations in all harbour sediment trap samples were below the PEL. The mean values for each harbour sediment trap sample can be used as an accurate historical baseline in future studies. Stormdrain samples with high trace metal levels were close to industrial and construction sites. The proximity of these outlets to recreational areas should be of concern to local authorities. Received: 28 August 1997 · Accepted: 15 December 1997     

Geochemical fractionation of Ni,Cu and Pb in the deep sea sediments from the Central Indian Ocean Basin: An insight into the mechanism of metal enrichment in sediment

Metal speciation study in combination with major element chemistry of deep sea sediments provided possible metal enrichment pathways in sediments collected from environmentally different locations of Central Indian Ocean Basin (CIB). Metal speciation study suggests that Fe–Mn oxyhydroxide phase was the major binding phase for Ni, Cu and Pb in the sediments. The second highest concentrations of all these metals were present within the structure of the sediments. Easily reducible oxide phase (within the Fe–Mn oxyhydroxide binding phases) was the major host for all the three metals in the studied sediments. Major element chemistry of these sediments revealed that there was an increased tendency of Cu and Ni to get incorporated into the deep sea sediment via the non-terrigenous Mn-oxyhydroxide fraction, whereas, Pb gets incorporated mostly via amorphous Fe-hydroxides into the sediment from the CIB. This is the first attempt to provide an insight into the mechanism of metal enrichment in sediment that host vast manganese nodule.     

Controls of facies and sediment composition on the diagenetic pathway of shallow-water Heterozoan carbonates: the Oligocene of the Maltese Islands

Relatively few studies have so far addressed diagenetic processes in Heterozoan carbonates and the role that sediment composition and depositional facies exert over diagenetic pathways. This paper presents a study of Oligocene shallow-water, Heterozoan carbonates from the Maltese Islands. We investigate stratigraphic distribution, abundance and timing of diagenetic features and their relationship to sediment composition and depositional facies. The studied carbonate rocks comprise rud- to packstones of the Heterozoan association predominantly containing coralline red algae, bryozoans, echinoids and benthic foraminifers. XRD analyses show that all high-Mg calcite has been transformed to low-Mg calcite and that no aragonite is preserved. Diagenetic processes include dissolution of aragonitic biota, neomorphism of high-Mg calcitic biota to low-Mg calcite and cementation by fibrous, bladed, epitaxial and blocky cements. Stable isotopes on bulk rock integrated with petrographic data suggest that the study interval was not exposed to significant meteoric diagenesis. We interpret early cementation to have taken place in the marine and marine burial environment. The distribution and abundance of early diagenetic features, determining the diagenetic pathway, can be related to the primary sediment composition and depositional texture. Sorting and micrite content are important controls over the abundance of diagenetic features.     

Metal retention in a thin karstic soil, Christian County, Missouri

 The response of a Wilderness cherty loam series soil to repeated dosages of metals (as sewage sludge) using a two-step sequential extraction procedure was investigated. Variations in metal content between amended and control soils were related to organic matter, clay content, and clay mineralogy. Of the four metals investigated, Cu was found to accumulate in the top 20 cm of amended soils; Pb and Zn were present in even smaller amounts with respect to the control soils, and Cr concentrations were unaffected with respect to both depth and amendment. None of the metals indicated accumulation in deeper (>20 cm) parts of the soil profile. Overall, results suggest that the metals remobilize in the top 20 cm, being readily uptaken by the fescue grass growing in this lot. Precipitation of insoluble forms of metal into deeper parts of the soil profile was proven unlikely based on the distribution of metal concentrations throughout the profile. Received: 15 December 1997 · Accepted: 23 March 1998     

Changes in mobility and speciation of heavy metals in clay-amended incinerator fly ash

The generation of municipal solid waste incinerator fly ash (MSWIF) has been increasing significantly over the recent past, and its disposal is problematic and costly due to high concentration of leachable heavy metals present in the material. This study explored a potential stabilization of MSWIF by blending with a natural sorbent material with low permeability, clay, and assessed the potential release of heavy metals from the stabilized mixtures under various simulated subsurface environments. The leachability of heavy metals such as Pb, Cd, Cr, Zn and Cu in the MSWIF-clay mixtures cured for 1 to 360 days was investigated by performing leaching tests and sequential chemical extractions (SCE). Leaching tests were performed at acidic, neutral and alkaline pH values. The leaching test results suggested that the natural clay could turn the MSWIF into non-hazardous material. All the MSWIF-clay mixtures demonstrated leaching behavior different from that of the original MSWIF. SCE results revealed that the acidic and reducing conditions were the most unfavorable to the immobilization of the heavy metals in the stabilized MSWIF-clay matrix. Conversely, the oxidizing and alkaline conditions were not critical to the stabilized MSWIF-clay mixtures. Apparently, clay in the mixtures could function as an adsorptive micro-barrier to retain the heavy metals within the MSWIF-clay matrices.     

Acid leached analyses of stormdrain and harbor sediments, New Zealand

 Sediments from stormdrain catchments in Wellington city and sediment traps from Wellington Harbor were sampled for trace metal content. Samples were analyzed for acid leached metal content by extraction with 0.11 mol acetic acid l^–1 and using ICP-MS. Cu and Zn levels in harbor sediment traps increased towards the periphery of the harbor, while Pb levels adjacent to a road almost doubled. In general, areas of light industry in the Inner City stormdrain catchments exhibited higher acid leached metal concentrations. However, large-scale renovation work probably contributed to point sources of high metal levels. The proximity of stormdrain outlets to recreational activities, such as wharf fishing and shellfish gathering, should be of prime concern to local authorities. Some positive correlations are found between acid leached and total metal levels. These may prove useful for assessing the biological impact of significant increases in total metal concentrations in the vicinity of Wellington Harbor. Significant savings in the time and costs of analyses may be achieved. Received: 27 February 1998 · Accepted: 27 April 1998     

Evolution of heavy-metal profiles in river Weser Estuary sediments,Germany

Studies of heavy metal concentrations in porewaters and in sediments from the Weser Estuary, Germany, indicate that the depth distribution of Mn, Cd, and Cu in the solid phase is predominantly influenced by the subsurface redox regime, while Ni shows only moderate alteration. Based on solid-phase heavy metal data from eight locations in the study area, linear regressions of Fe, Mn, Cu, Ni, and Cd on Al allowed differences between the initial metal concentration and the concentration preserved in the sediments to be predicted. We calculate that, due to early diagenetic processes, Mn is enriched to 145 percent, while Cu and Cd are depleted to 71 percent and 46 percent, respectively, of the initial metal concentration in the near-surface sediment. Maximum depletion of Cd (84 percent), Cu (68 percent), Mn (54 percent), and Ni (24 percent) concentrations in the sediment, observed at a restricted area downcore, indicate the importance of post-depositional processes to metal preservation in the sediment. Without knowledge of the quantitative effects of diagenetic reactions on the preservation of metal concentrations in sediments, the depth distribution of metals in sediment cores may be misinterpreted as the effect of human activities.     

Heavy metals in sediments of the Tecate River, Mexico

Ten sites along the Tecate River, Mexico were sampled to evaluate the cadmium, lead, nickel and chromium concentrations in sediments. The result shows contamination for cadmium in most of the sites, where two sites were class 4 (polluted to strongly polluted) according to geoaccumulation index proposed by Muller. Two sites were found polluted for all the heavy metals analyzed (Cr, Cd, Pb and Ni), indicating the effect of anthropogenic activities. A correlation between Ni and Cd concentration had been found indicating a common source. These metals are usually used in electroplating industry. The results of this study can be used for decision makers to prioritize measures to control the pollution for these metals.     

Accumulation and speciation of selenium in evaporation basins in California,USA

The accumulation of selenium in evaporation basins (or ponds) in the San Joaquin Valley, California is of a great concern due to its potential hazards to environments. In this study, the accumulation, speciation and concentrations of Se were examined in waters as well as sediments in a system of the evaporation ponds. A significant decrease in the total dissolved Se concentration in Cell 1 in which drainage water with higher Se concentration was pumped from Inlet Channels indicated that the immobilization of Se was active in the Cell 1 and resulted in the higher Se concentration in sediments compared to the terminal cell such as Cell 9. The percentage of reduced Se species such as selenite [Se(IV)] and org-Se of total Se in drainage waters was also found increased in Cell 1 compared to Inlet Channels. The total dissolved Se concentrations in water along flow paths from Cell 1 were relatively constant except for terminal cells such as Cells 9 and 10, which showed higher total dissolved Se concentrations due to evapoconcentration. The percentage of reduced Se forms of total Se was inversely proportional to the percentage of Se(VI) depending on the redox condition of evaporation ponds along the flow paths. Sequential extractions of Se species in sediments indicated that organic associated Se and elemental Se were prevalent forms in sediments in the ponds system. The higher concentrations of elemental Se and organic associated Se in sediments in Cell 1 indicated that the immobilization of Se was active in the sediments compared to Cell 9, while the percentage of both fractions of total Se in sediments in Cells 1 and 9 was relatively constant. The organic materials from algae might provide carbon sources for Se reduction and Se sink in sediments in its elemental and organic associated forms.     

Bioaccumulation of heavy metals in oyster (Crassostrea virginica) tissue and shell

Oysters and sediment have been collected from most major US Gulf of Mexico bays and estuaries each year since 1986. Selected samples of oyster soft tissue, shell and sediments were analyzed for Cd, Cr, Cu, Fe, Mn, Pb, and Zn for this study. Concentrations varied considerably from place to place but ratios of metals remained relatively constant. Cu and Zn are greatly enriched in oyster tissues, which is related to their physiological function. Cd is enriched in oyster shell because of the easy substitution between Cd and Ca. The concentrations of Pb and Cr in oysters are significantly lower than that in sediment, suggesting a good discrimination against these metals by oysters. Metal variations are a result of both nature and human activity. Received: 13 September 1999 · Accepted: 8 December 1999     

Historical changes in heavy metals in the Yangtze Estuary, China

A 6-m-long core was used to examine historical changes in heavy metals on tidal flats in the Yangtze Estuary, China. Over the last 100 years, human impact was minimal. However, over the last few decades, vertical metal concentrations have been affected by human activities such as local industrialization, urbanization and construction of major sewage outlets. Copper, lead and arsenic were identified as contaminants in the Yangtze Estuary on the basis of national pollution standards and a comparison of metals in the upper core with those in the lower core.     

Heavy metal distribution in karst soils from Croatia and Slovakia

With the use of the optimised three-step BCR sequential-extraction procedure it was possible to assess the mobility of selected elements in soil profiles from Croatian and Slovakian karst terrains. The soils in the Croatian karst were enriched in Cr, Ni, V, Mn, Cu, Cd and Mo, while soils from the Slovak Karst had high Pb and Zn concentrations. It was determined that the elements were most readily mobilised from the topsoil and the degree of mobility decreased with depth. Cr and Ni were mainly bound to the residual fraction, and Pb in the oxidisable fraction. Cu mobility was high in samples treated with agrochemicals throughout the soil profile.