Mercury distribution in abiotic and biological compartments within several estuarine systems from Argentina: 1980-2005 period

Total mercury contents from both abiotic and biological compartments within several estuaries from Argentina have been studied since the 1980s. The assessment of mercury occurrence in surface sediments, suspended particulate matter and crab and fish species from Mar Chiquita coastal lagoon, Bahía Blanca estuary and Samborombón Bay (in La Plata river estuary) are included in the present study. All samples were analyzed through Cold Vapor-Atomic Absorption Spectroscopy, following internationally standardized methods. In all cases analytical quality was checked against international reference materials. During the 1980s, Hg contents in sediments and SPM, as well as in edible fish species from Bahía Blanca estuary were significantly higher (p<0.01) than those of the 1990s and 2000s, and the large industrial nucleus located in the northern margin of this estuary was elsewhere identified as the main source of this metal. A permanent monitoring program carried out in 1986 and that is being implemented up to the present has demonstrated that Hg concentration values have significantly decreased (p<0.01) compared to the values of the 1980s. Both, Mar Chiquita coastal lagoon and Samborombón Bay have intermediate mercury levels in their biological compartments. In both cases, the possible occurrence of remote sources of this metal was considered. Even though, Hg values as determined in sediments and suspended particulate matter from Samborombón Bay were the highest ones for the whole analyzed period. Both mercury bioaccumulation and biomagnification processes were evaluated in the studied estuaries, as well as the potential qualification of estuarine foodstuffs for human consumption.     

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.     

Polycyclic aromatic hydrocarbons in suspended particulate matter and sediments from the Pearl River Estuary and adjacent coastal areas, China

The spatial distribution, composition, and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments and suspended particulate matter (SPM) from the Pearl River Estuary and adjacent coastal areas were examined. Total PAH concentrations varied from 189 to 637 ng/g in sediments and 422 to 1,850 ng/g in SPM. PAHs were dominated by 5,6-ring compounds in sediments and by 2,3-ring compounds in SPM samples. Assessment of PAH sources suggested that biomass and coal combustion is the major PAH source to the outer part of the estuary sediments and that petroleum combustion is the major PAH source to the inner part of estuary sediments. As for SPM samples, PAH isomer pair ratios indicated multiple (petroleum, petroleum combustion, and biomass and coal combustion) PAH sources, and significant temporal variations could exist for the sources of water column PAHs in the study area. The distribution of perylene in SPM samples indicated that the river was the dominant source of perylene in SPM and that perylene could be taken as an index to assess the contribution of river inflow to the total PAHs in SPM samples. The high concentration of perylene in the sediment was indicative of an in situ biogenic origin.     

Distribution of polycyclic aromatic hydrocarbons in water, suspended particulate matter and sediment from Daliao River watershed, China

This study investigated the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in surface water, suspended particulate matter (SPM) and sediment of Daliao River watershed composed of the Hun River, Taizi River, and Daliao River. The sources of PAHs were evaluated employing ratios of specific PAHs compounds and principal component analysis (PCA). The total concentrations of PAHs ranged from 946.1 to 13448.5 ng l(-1) in surface water, from 317.5 to 238518.7 ng g(-1) dry weight in SPM, and from 61.9 to 840.5 ng g(-1) dry weight in sediments. The levels of PAHs are relatively higher in water and SPM, and lower in sediments, in comparison with those reported for other rivers and marine systems around the world. The composition of PAHs in these mediums was mainly 4-6 rings PAHs. The higher contents of low molecular weight PAHs in the water and SPM suggest a relatively recent local source of PAHs, entered into the river via wastewater discharge and atmospheric way. On the other hand, the heavy pollution of PAHs in sediment and water near heavy industrial area suggests that PAHs have been released from industrial wastewater.     

Trace metal behaviour in the Conwy estuary,North Wales

The distribution of trace metals Zn, Ni, Mn, Fe, Cu, Pb, Cd and Cr between suspended particulate matter (SPM) and water in the Conwy estuary, North Wales, has been studied in three surveys in 1998. Dissolved Cu and Mn showed some monthly variations. Most of the dissolved trace metals displayed a negative association with salinity, indicating rivers as a major source of inputs for them. Particulate Zn, Mn and Fe showed a decreasing concentration seaward, whilst the levels of Ni, Cu, Cr and Pb increased with salinity. SPM concentration was the most important variable significantly related to trace metal concentrations in SPM, with an inverse relationship between the two parameters. This was explained by the relative enrichment of trace metals in fine particles at low SPM concentrations and relative depletion of trace metals in coarse particles at high SPM concentrations. Particulate Zn, Mn and Pb were dominated by the fraction available to acetic acid (non-detrital), whilst particulate Ni, Fe and Cr were dominated by the fraction available to nitric acid (detrital). The partition coefficient of trace metals between SPM and water declined with increasing SPM concentration, consistent with the so-called "particle concentration effect". Such a phenomenon may be explained by the presence of fine particles (including colloids) enriched with trace metals at low SPM concentrations, and the salinity-induced desorption.     

The influence of inputs to the Firth of Forth on the concentrations of trace metals in coastal waters

The distribution of copper, lead and cadmium in dissolved and particulate phases has been investigated in the Firth of Forth, Scotland, an embayment of the North Sea. The effect of riverine and anthropogenic trace metal inputs on concentrations in the Firth of Forth and adjacent North Sea is examined. For the dissolved phase the effect of such inputs is confined to the immediate area of discharge. Concentrations in the outer Firth are indistinguishable from those in coastal waters of the North Sea, ca. Cu, 0.2 microgdm(-3) (3.1nm); Pb, 0.025 microgdm(-3) (0.12nm) and Cd, 0.020 microgdm(-3) (0.18nm). There is evidence that particulates enhanced in trace metals, relative to bottom sediments, are leaving the Forth and entering the North Sea. Predictions of the total metal concentrations in the waters of the inner Firth, based on riverine, industrial and sewage associated inputs, show reasonable agreement with observed values.     

Effect of overlying water pH, dissolved oxygen, salinity and sediment disturbances on metal release and sequestration from metal contaminated marine sediments

Experiments were undertaken to examine the key variables affecting metal release and sequestration processes in marine sediments with metal concentrations in sediments reaching up to 86, 240, 700, and 3000 mg kg(-1) (dry weight) for Cd, Cu, Pb and Zn, respectively. The metal release and sequestration rates were affected to a much greater extent by changes in overlying water pH (5.5-8.0) and sediment disturbance (by physical mixing) than by changes in dissolved oxygen concentration (3-8 mg l(-1)) or salinity (15-45 practical salinity units). The physical disturbance of sediments was also found to release metals more rapidly than biological disturbance (bioturbation). The rate of oxidative precipitation of released iron and manganese increased as pH decreased and appeared to greatly influence the sequestration rate of released lead and zinc. Released metals were sequestered less rapidly in waters with lower dissolved oxygen concentrations. Sediments bioturbated by the benthic bivalve Tellina deltoidalis caused metal release from the pore waters and higher concentrations of iron and manganese in overlying waters than non-bioturbated sediments. During 21-day sediment exposures, T. deltoidalis accumulated significantly higher tissue concentrations of cadmium, lead and zinc from the metal contaminated sediments compared to controls. This study suggests that despite the fact that lead and zinc were most likely bound as sulfide phases in deeper sediments, the metals maintain their bioavailability because of the continued cycling between pore waters and surface sediments due to physical mixing and bioturbation.     

Mercury,zinc, and copper accumulation in mangrove sediments surrounding a large landfill in southeast Brazil

The accumulation of Hg, Zn, and Cu was evaluated in mangrove sediments located between a large, 20-years-old landfill and waters of Guanabara Bay (southeast Brazil). The contamination history of the area provides substantial evidence that metal accumulation in the study site is influenced by past metal emissions from multiple sources (e.g. contaminated rivers and the landfill surrounding the site). At the southern part of the site, metal levels are up to 890 ng g(-1) Hg, 850 microg g(-1) Zn, and 58 microg g(-1) Cu. Enrichment factors and excess (background-deducted) concentration inventories show a high spatial variability of metal contamination and storage in the site, with differences often by a factor higher than two within a sampling station and higher than five between sampling stations. These contrasts are attributable to a coupling between spatial variability of anthropogenic metal input and metal behavior and retention within the sediments. Results indicate that during the last few decades mangrove sediments retained a substantial part of metal emissions to the site, probably reducing the metal transport to Guanabara Bay waters, and suggest the suitability of mangrove ecosystems as physical and biogeochemical barriers to metal contaminant transport.     

Polychlorinated biphenyl congeners and organochlorine insecticides in the water column and sediments of Daya Bay, China.

Samples of sub-surface water, suspended particulate matter (SPM) and surface sediments collected from Daya Bay, China have been analysed for 12 polychlorinated biphenyl (PCB) congeners and 18 organochlorine insecticides, using gas chromatography electron capture detection. Total PCB levels varied from 91.1 to 1355.3 ng l-1 in water and from 0.85 to 27.37 ng g-1 dry weight in sediments. The levels of total organochlorine insecticides were in the range 143.3-5104.8 ng l-1 in water and 2.43-86.25 ng g-1 dry weight in sediment. None of the target compounds were detected in SPM. The levels of total hexachlorocyclohexanes in water varied from 35.5 to 1228.6 ng l-1, whilst in sediments they ranged from 0.32 to 4.16 ng g-1 dry weight. For the sum of dichlorodiphenyltrichloroethanes (DDTs), their levels were in the range 26.8-975.9 ng l-1 in water, and 0.14-20.27 ng g-1 dry weight in sediments. The distribution profiles of these contaminants in water and sediments suggest that there are a number of sources contributing to total contaminant burden in the bay, including soil runoffs, wastewater discharges, sewage outfalls and shipping activites. Ratios of DDT/(DDE + DDD) in the water and sediments indicate recent inputs of such chemicals into the day. The results, therefore, provide important information on the current contamination status of a key aquacultural area in China, and point to the need for urgent actions to stop the use of persistent agrochemicals such as DDT and lindane.     

Distribution and coassociations of trace elements in soft tissue and byssus of Mytilus galloprovincialis relative to the surrounding seawater and suspended matter of the southern part of the Korean Peninsula

The concentrations of Cd, Co, Cu, Cr, Fe, Hg, Mn, Ni, Pb, Sn, Ti and Zn were analyzed by AAS, ICP MS and AFS in soft tissues and byssal threads of Mytilus galloprovincialis from Masan Bay and Ulsan Bay, Korea. Spatial variations in metal concentrations were found. The levels of Cd, Pb, Hg, Cu, Zn, Co and Mn were very high in the mussels from Ulsan Bay (Sts. U1, U2) and comparable with elevated concentrations of these elements in Mytilus sp. reported to date for other geographical areas. Seasonal differences in some metal concentrations were also observed. These variations may be caused by factors such as: a large difference in seawater temperature, food supply for the mussel population and/or freshwater runoff of particulate metal to the coastal water and weight changes brought about by gonadal development and the release of sexual products. Pb, Cu, Zn, Co, Ni, Fe and Mn were more enriched in byssal threads than in the soft tissues, hence the byssus seems to be more sensitive in reflecting the availabilities of trace metals in the ambient waters. Concentrations of trace metals varied with respect to the size of mussels and season, depending on many factors like sexual development, and seawater temperature, etc. The levels of some trace metals in seawater, especially in suspended matter were correlated significantly with those in soft tissues and byssal threads. There were spatial variations in metal concentrations in the soft tissue and byssus attributed to different sources of trace elements located near the sampling sites. There were significant relationships between concentrations of some metals (Cd, Cu, Pb, and Zn) in mussel soft tissues and byssal threads and suspended matter. This suggests that M. galloprovincialis can be used as a sensitive biomonitor for the availabilities of trace elements in the coastal waters off Korea.     

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.     

Trace metal distribution in sediments of the Pearl River Estuary and the surrounding coastal area, South China

Surface sediments and sediment cores collected at the Pearl River Estuary (PRE) and its surrounding coastal area were analysed for total metal concentrations, chemical partitioning, and Pb isotopic compositions. The distribution of Cu, Cr, Pb, and Zn demonstrated a typical diffusion pattern from the land to the direction of the sea. Two hotspots of trace metal contamination were located at the mixed zone between freshwater and marine waters. The enrichment of metals in the sediments could be attributed to the deposition of the dissolved and particulate trace metals in the water column at the estuarine area. The similar Pb isotopic signatures of the sediments at the PRE and its surrounding coastal area offered strong evidence that the PRE was a major source of trace metals to the adjacent coastal area. Slightly lower (206)Pb/(207)Pb ratios in the coastal sediments may indicate other inputs of Pb in addition to the PRE sources, including the inputs from Hong Kong and other parts of the region.     

Metal accumulation in sediments and benthic invertebrates in lakes of Latvia

The concentrations of cadmium, lead, nickel and copper in waters, sediments (total metal concentrations and their speciation forms) and benthic macroinvertebrates in 11 lakes of Latvia were determined using atomic absorption spectroscopy. Metal concentrations in lake waters, sediments and biota were compared with water chemistry. Compared to total concentrations, metal speciation forms in sediments were better correlated with respective metal concentrations in invertebrates. Therefore, the evaluation of potential metal bioaccumulation should consider metal speciation. The mean concentrations of trace metals in benthic invertebrates in Latvia were much lower than in other countries, which can be explained by comparatively lower anthropogenic loads. However, local areas of anthropogenic impacts were evident.     

Stomata and plant water relations: does air pollution create problems?

Suspended particulate matter (SPM), sandy sediments and Asiatic clams were collected at seven sites along 150 km of the Río de la Plata coast to assess the magnitude of trace metal pollution in the area. Metal concentrations in SPM (Cu: 7.4-109; Cr: 75-408; Mn: 525-1341 microg(-1)), sediments (Cr: 16-27; Zn: 26-99; Mn: 221-489 microg(-1)) and bivalves (Cd: 0.5-1.9; Ni: 1.3-6.4; Cr: 1.3-11; Mn: 15-81; Cu: 28-89; Zn: 118-316 microg g(-1)) are comparable to those reported for other moderately polluted world rivers. Cu levels in Asiatic clams are among the highest, similar to those reported for heavily polluted sites. SPM Cu and Cr concentrations displayed a clear geographical trend with values increasing with proximity to major urban centers. Sediments showed a less clear pattern possibly due to their coarse nature (>98% sand) and higher proportion of mineral-associated residual metals. The clams showed a complex pattern due to the variability introduced by size-related factors and the natural dynamics of SPM in the estuary. Cr and Mn showed an apparent reverse industrial trend with higher concentrations in clams collected at distant stations near the turbidity maximum zone, possibly reflecting enhanced particle retention. Cu, Cd and Ni showed no clear geographical pattern, whereas Zn increased in the clams collected in the most industrialized area. A significant relationship with clam size was observed for Cu (positive) and Zn (negative) suggesting different physiological requirements for both metals with age. A principal component analysis confirmed these geographical and size-related trends.     

Pharmaceuticals in settleable particulate material in urban and non-urban waters

Wastewater treatment plants (WWTP) are important sources of settleable particulate material (SPM), heading to sediments with natural suspended solids. To date, there is little information about the fate of pharmaceuticals in sediment systems. In this study, the objective was to determine if pharmaceuticals are detected in SPM at locations near WWTPs or even in rural areas, thus being susceptible for sedimentation.SPM samples were collected from 10 sites in Finland, grouped as reference, rural and wastewater effluent sites. SPM collectors were placed about 35 cm above bottom for about 2 months during summer. After extraction, a set of 17 pharmaceuticals was analyzed.Several pharmaceuticals were detected in SPM accumulated at sites next to WWTPs. The concentration of citalopram was notably high (300-1350 ng g⁻¹ dw). Also bisoprolol and ciprofloxacin were detected at high concentrations (6-325 and 9-390 ng g⁻¹ dw, respectively). In contrast, none of the pharmaceuticals were detected from reference sites and only two were found from a single rural site.There is no previous information about the presence of pharmaceuticals in SPM. The results showed that pharmaceuticals are sorbed to particles in WWTP and nearby, eventually ending up in sediments. These results also indicate that pharmaceuticals are not markedly contaminating sediments of rural areas in Finland.     

Trace metals in flounder, Platichthys flesus (Linnaeus, 1758), and sediments from the Baltic Sea and the Portuguese Atlantic coast

Trace metals were examined in the muscle tissue of flatfish species of flounder, Platichthys flesus (Linnaeus, 1758), sediments from two southern Baltic Sea sites (Gdańsk Bay and Ustecko-?ebskie as a reference) and in two areas of the Portuguese Atlantic coast (Douro River estuary and Atlantic fishing ground as a reference) to evaluate spatial differences in trace metals. Additionally, the accumulation of trace metals in flounder of different length classes was assessed. Flounder from the Gdańsk Bay area contained twofold more cupper (Cu), lead (Pb) and mercury (Hg) than did flounder from the Douro River estuary, but zinc (Zn) and cadmium (Cd) were at similar concentrations. The sediments from Gdańsk Bay contained significantly more Zn and threefold more Cd, while concentrations of Cu and Pb were twofold lower. The concentrations of metals in the sediments did not correlate with those in the flounder. Spatial differences were noted in metal concentrations in flounder from the southern Baltic Sea and the Portuguese Atlantic coast as well as within these regions, with higher concentrations in the flounder from the Baltic Sea Gdańsk Bay. The flounder in length class 25–30 cm from Gdańsk Bay contained metal concentrations comparable to those of class 40–45 cm specimens from the Atlantic coast. The accumulation of metals in flounder length classes differed in the two regions.     

Occurrence and behaviour of selected hydrophobic alkylphenolic compounds in the Danube River

Six hydrophobic alkylphenolic compounds were investigated for the first time simultaneously in four different matrices in the Danube River. Maximum sediment concentrations were 2.83, 2.10, 0.28, and 0.035 mg kg⁻¹ for nonylphenol, nonylphenol monoethoxylate, nonylphenol diethoxylate and octylphenol. Maximum levels in suspended particulate matter (SPM) were 0.18, 0.12, 0.10, and 0.003 mg kg⁻¹. No correlation between concentrations in SPM and sediments was found. Octylphenol monoethoxylate and octylphenol diethoxylate were recorded only in sediment at one location. In mussels and water only nonylphenol and octylphenol were found. Nonylphenol concentrations in mussels (up to 0.34 mg kg⁻¹) correlate with concentrations found in SPM and indicate a slight bioaccumulation. Concentrations in water were close to the limit of quantification. We assume in situ formation of nonylphenol monoethoxylate and nonylphenol in sediments at some locations. In some cases nonylphenol in sediments exceeded the provisional EU environmental quality standards.     

The effect of aged litter materials on polyatomic ion concentrations in fractionated suspended particulate matter from a broiler house

Inorganic emissions from livestock production and subsequent deposition of these ions can be a major source of pollution, causing nitrogen enrichment, eutrophication, acidification of soils and surface waters, and aerosol formation. In the poultry house, ammonia and hydrogen sulfide emissions can also adversely affect the health, performance, and welfare of both animals and human operators. The persistence and long life expectancy of ammonia, odors and toxic pollutants from poultry houses may be due to the ability of suspended particulate matter (SPM) to serve as carriers for odorous compounds such as ammonium ions and other inorganic compounds (e.g., phosphate, sulfate, nitrate, etc.). SPM is generated from the feed, animal manure, and the birds themselves. A large portion of odor associated with exhaust air from poultry houses is SPM that has absorbed odors from within the houses. Understanding the fate and transport processes of ammonia and other inorganic emissions in poultry houses is a necessary first step in utilizing the appropriate abatement strategies. In this study, the examination and characterization of ammonium ions, major components of odors and toxic gases from poultry operations, and other ions in suspended particulate matter in a broiler house were carried out using particle trap impactors. The SPM from the particle trap impactors was extracted and analyzed for its ionic species using ion chromatography (IC). The results showed concentrations of polyatomic ions in suspended particulate matter were found to increase with successive flocks and were highly concentrated in the larger size particulate matter. In addition, the ions concentrations appeared to reach a maximum at the middle of flock age (around the fourth week), tapering off toward the end in a given flock (possibly due to ventilation rates to cool off larger birds). Thus, it can be inferred that aged of bedding materials affects the ionic concentrations in aerosol particulate matter more than the age of the birds.

Implications: In the poultry house, toxic gas emissions can adversely affect the health, performance, and welfare of both animals and human operators. The persistence of these toxic pollutants from poultry houses may be due to the ability of suspended particulate matter (SPM) to serve as carriers for these compounds (inorganic ions). Our study showed that polyatomic ions in suspended particulate matter were found to increase with successive flocks and were highly concentrated in the larger size SPM. Understanding the effect of management practices on poultry air emissions will lead to innovative best management practices to safeguard the health and welfare of the animals as well as those of the poultry operators, along with reducing the impact of potential air pollution on the environment.     

The effect of manipulating sediment pH on the porewater chemistry of copper- and zinc-spiked sediments

Spiking of sediment with metal cations that readily hydrolyse causes the sediment pH to decrease. Displaced iron and manganese also oxidise and hydrolyse, further lowering sediment pH. The lower pH of metal-spiked sediments requires a subsequent sediment neutralisation. This research compared the pH adjustment of Cu- and Zn-spiked sediments using single and multiple additions of 1M NaOH. Sediment pH, redox potential, and porewater metal concentrations were monitored over 40 days. Depth profiles were also measured to investigate stratification. A single pH adjustment to pH 7 and 8 initially counteracted the pH change caused by metal additions, however, pH continued to decrease slowly thereafter. Multiple pH adjustments diminished porewater Cu, Zn and Fe concentrations to a greater extent than a single pH adjustment, but the ongoing oxidative precipitation of porewater metals continued to consume OH(-) ions and impede pH maintenance. Displacement of high iron(II) concentrations and the opposing rates of iron(II) oxidative precipitation and bacterially-mediated iron(II) production, affected the partitioning of the added metals between the sediment and pore water. Despite similar pH over the spiked-metal concentration gradient following pH adjustment, sediments spiked with higher metal concentrations produced lower porewater Fe concentrations, possibly due to toxicity to iron(III) oxyhydroxide reducing bacteria. Distinct stratification of redox potential and dissolved Fe and Cu developed over a depth of 6cm during the 40-day equilibration period. Recommendations are provided on methods for preparing metal-spiked sediments in which the partitioning of metals between dissolved and particulate phases better resembles that of in situ (field) metal-contaminated sediments.