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.     

Quantifying sediment-associated metal dispersal using Pb isotopes: Application of binary and multivariate mixing models at the catchment-scale

In this study Pb isotope signatures were used to identify the provenance of contaminant metals and establish patterns of downstream sediment dispersal within the River Maritsa catchment, which is impacted by the mining of polymetallic ores. A two-fold modelling approach was undertaken to quantify sediment-associated metal delivery to the Maritsa catchment; employing binary mixing models in tributary systems and a composite fingerprinting and mixing model approach in the wider Maritsa catchment. Composite fingerprints were determined using Pb isotopic and multi-element geochemical data to characterize sediments delivered from tributary catchments. Application of a mixing model allowed a quantification of the percentage contribution of tributary catchments to the sediment load of the River Maritsa. Sediment delivery from tributaries directly affected by mining activity contributes 42-63% to the sediment load of the River Maritsa, with best-fit regression relationships indicating that sediments originating from mining-affected tributaries are being dispersed over 200 km downstream.     

Assessment of heavy metal contamination in Hindon River sediments: a chemometric and geochemical approach

The aim of this study was to assess the level of heavy metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in the surface sediments of the Hindon River, India that receives both treated and untreated municipal and industrial discharges generated in and around Ghaziabad, India. Mean metals concentrations (mg kg⁻¹) were in the range of; Cu: 21.70-280.33, Cd: 0.29-6.29, Fe: 4151.75-17318.75, Zn: 22.22.50-288.29, Ni: 13.90-57.66, Mn: 49.55-516.97, Cr: 17.48-33.70 and Pb: 27.56-313.57 respectively. Chemometric analysis was applied to identify contribution sources by heavy metals while geochemical approaches (enrichment factor and geo-accumulation index) were exploited for the assessment of the enrichment and contamination level of heavy metals in the river sediments. Chemometric analysis suggested anthropic origin of Cu, Cd, Pb, Zn, and Ni while Fe showed lithogenic origin. Mn and Cr was associated and controlled by mixed origin. Geochemical approach confirms the anthropogenic influence of heavy metal pollution in the river sediments. The study suggests that a complementary approach that integrates chemometric analysis, sediment quality criteria, and geochemical investigation should be considered in order to provide a more accurate appraisal of the heavy metal pollution in river sediments. Consequently, it may serve to undertake and design effective strategies and remedial measures to prevent further deterioration of the river ecosystem in future.     

Long-term copper partitioning of metal-spiked sediments used in outdoor mesocosms

Understanding the effects of sediment contaminants is pivotal to reducing their impact in aquatic environments. Outdoor mesocosms enable us to decipher the effects of these contaminants in environmentally realistic scenarios, providing a valuable link between laboratory and field experiments. However, because of their scale, mesocosm experiments are often complex to set up and manage. The creation of environmentally realistic conditions, particularly when using artificially contaminated sediment, is one issue. Here, we describe changes in geochemistry over 1.5 years of a sediment spiked with four different concentrations of copper, within a large freshwater mesocosm facility. The spiking procedure included proportional amendments with garden lime to counteract the decreases in pH caused by the copper additions. The majority of copper within the spiked mesocosm sediments partitioned to the particulate phase with low microgram per liter concentrations measured in the pore waters and overlying waters. The minimum partition coefficient following equilibration between pore waters and sediments was 1.5?×?10⁴ L/kg, which is well within the range observed for field-contaminated sediments (1?×?10⁴ to 1?×?10⁶ L/kg). Recommendations are made for the in situ spiking of sediments with metals in large outdoor mesocosms. These include selecting an appropriate sediment type, adjusting the pH, allowing sufficient equilibration time, and regular mixing and monitoring of metal partitioning throughout the experimental period.     

Metal bioavailability and toxicity through a sediment core.

Sediment cores from Richard Lake near Sudbury, Ontario, were sectioned and analyzed for total metal content, plus metal bioavailability and toxicity to Hyalella azteca (after equilibration with oxygenated overlying water). Strong and similar sediment profiles were observed for Cd, Co, Cu and Ni in the sediment. However, these differed from metal bioavailability profiles (bioaccumulation by Hyalella and metals in overlying water). Bioavailability profiles for Cu also differed from those for Cd, Co or Ni. The deepest sediment layers, deposited prior to industrial development, were non-toxic. Sediment toxicity was attributed to Ni dissolution into overlying water. Moreover, differential bioavailability of Ni in surface and deeper sediment layers was observed. This can affect the interpretation of toxicity data for sediments collected by different methods (e.g. core vs. grab samples). Based on Pb-210 dating and trends in Ni in the core, chronic toxicity of surface sediments from Richard Lake might approach non-toxic levels in about 15 years.     

Indirect effect of nutrient accumulation intensified toxicity risk of metals in sediments from urban river network

The levels of metals in sediments of urban river ecosystems are crucial for aquatic environmental health and pollution assessment. Yet little is known about the interaction of nutrients with metals for environmental risks under contamination accumulation. Here, we combined hierarchical cluster, correlation, and principal component analysis with structural equation model (SEM) to investigate the pollution level, source, toxicity risk, and interaction associated with metals and nutrients in the sediments of a river network in a city area of East China. The results showed that the pollution associated with metals in sediments was rated as moderate degree of contamination load and medium-high toxicity risk in the middle and downstream of urban rivers based on contamination factor, pollution load index, and environmental toxicity quotient. The concentration of mercury (Hg) and zinc (Zn) showed a significant correlation with toxic risks, which had more contribution to toxicity than other metals in the study area. Organic nitrogen and organic pollution index showed heavily polluted sediments in south of the study area. Though correlation analysis indicated that nutrients and metals had different input zones from anthropogenic sources in the urban river network, SEM suggested that nutrient accumulation indirectly intensified toxicity risk of metals by 13.6% in sediments. Therefore, we suggested the combined consideration of metal toxicity risk with nutrient accumulation, which may provide a comprehensive understanding to identify sediment pollution.

Toxicity rate of metals in sediments from urban river network indirectly intensified by nutrients accumulation

     

Distribution and accumulation of heavy metals in the sediments of Kaohsiung Harbor, Taiwan

The distribution, enrichment, and accumulation of heavy metals in the sediments, especially those at the vicinity of tributary estuaries of Kaohsiung Harbor, Taiwan were investigated. Sediment samples from six locations in the Kaohsiung Harbor were collected quarterly in the period from 2002 to 2005 and characterized for metal content (e.g., Hg, Pb, Cd, Cr, Cu, Zn and Al), water content, organic matter, total nitrogen, total phosphorous, total grease, and grain size. Results showed that metal concentrations varied from 0.58 mg kg(-1) for Cd to 596 mg kg(-1) for Zn. Metal concentrations at the vicinity of river mouths were higher than those at other locations. All heavy metals studied, except Cr, had relatively high enrichment factors and geo-accumulation indices in the estuaries. Moreover, metal concentrations correlated closely to the physical-chemical properties of the sediments, which strongly suggested the influence of industrial and municipal wastewaters discharged from the neighboring industrial parks and river basins. Results would help develop strategies for pollution control and sediment remediation of Kaohsiung Harbor.     

底泥污染物释放动力学研究

采用模拟试验方式和新型微生物数量测定方法 ,研究了沼泽化湖泊底泥和受污染河流底泥在不同扰动状态下 ,底泥耗氧速率、氮和磷污染物释放动力学过程。结果表明 :( 1)底泥耗氧速率是同样条件下上覆水耗氧速率的 48倍 ,而在扰动状态下 ,底泥耗氧速率达到上覆水耗氧速率的 5 96— 93 6倍 ,扰动底泥显著增大其耗氧速率 ,底泥污染越严重 ,其耗氧速率越大 ,对水体产生的影响也越大。 ( 2 )扰动底泥可以显著增大底泥的氮磷释放速率 ,氮的释放受有机氮的氨化、氨氮的硝化、硝酸盐氮的反硝化以及氨氮被微生物吸收转化为有机氮等的影响 ;磷的释放过程受厌氧过程和底泥颗粒吸附的影响 ,耗氧速率高的底泥具有更大的氮磷释放潜力。 ( 3 )微生物数量在底泥污染物释放动力学中起着关键性作用 ,新型方法可以快速检测微生物总量。试验结果对于水环境的管理、受污染水体的修复 ,以及底泥的处理处置等都具有重要的指导意义     

Heavy metal pollution in sediments of the Pasvik River drainage

The purpose of this paper is to study the regional impacts of heavy metals (Ni, Cu, Co, Zn, Cd, Pb, Hg) on the watershed of the Pasvik River. On the basis of sediment investigations at 27 stations of the watershed, background concentrations of the heavy metals, vertical distribution of heavy metals in sediments, heavy metal concentrations in surface sediments, contamination degree, and risk index were determined. The atmospheric emissions of Ni, Cu, Co, Zn, Cd and Hg from the smelters and waste waters from tailing dams and mines of the Pechenganickel Company are likely to be the main sources of increasing concentrations observed in recent sediments of the lower river reaches. Lead showed a different pattern from the other heavy metals--increasing Pb concentrations in the upper sediment layers towards the Norwegian side.     

Assessment of tin and butyltin species in estuarine superficial sediments from Gipuzkoa,Spain

Ten superficial sediments from river estuaries of Gipuzkoa (North Spain) were collected and analyzed for nine metals (including tin, Sn) and butyltin compounds (monobutyltin, MBT; dibutyltin, DBT; tributyltin, TBT). Total metal concentration in the fine fraction (<63 micrometer) of the sediment was determined in aqua regia--hydrofluoric acid extracts by atomic absorption spectrometry. The butyltin species (BTs) were firstly extracted from the sediments with hydrochloric acid-methanol mixture. After derivatization with sodium tetraethyl borate, the organotin compounds were extracted by solid phase microextraction (SPME) in headspace mode. A fiber coated with 100 micrometer poly(dimethylsiloxane) was used for SPME. The organotin species were analyzed by gas chromatography-flame ionization detection. Analysis of the certified reference sediment (PACS-2) shown the suitability of the procedures for determination of metal contents and DBT-TBT species in contaminated sediments. Factorial analysis was used to examine the main sources of metals. Three factors represented more than 89% of the total variance of the metal system, and the Sn was related with Cu-Zn-Pb suggesting the same pollution source. The BTs concentrations in the area were high (TBT ranged from 0.05 to 5.48 mg Sn kg(-1)). The percentage of total butyltin species ( summation operator BTs) respect to the total Sn amount was higher than 4% in all the sediments, showing in the Bidasoa river estuary a remarkable value higher than 20%. Hence, the studied estuarine sediments reflect a pollution that is related with historical industrial and fishing activities of the area.     

Processes controlling metal transport and retention as metal-contaminated groundwaters efflux through estuarine sediments

Factors affecting the transport and retention of Cd, Cr, Cu, Ni, Pb and Zn in acidic groundwaters as they pass through estuarine sediments were investigated using column experiments. Acidic groundwaters caused the rapid dissolution of iron sulfide (AVS) and other iron and manganese phases from sediments that are important for metal binding and buffering. Metal breakthrough to overlying water occurred in the order of Ni>Zn>Cd>Cu>Cr/Pb. Metal transport increased as the sediment permeability increased, reflecting the low resistance to flow caused by larger sand-sized particles and the decreased abundance of metal adsorption sites on these materials. Metal mobility increased as the groundwater pH decreased, as flow rate or metal concentrations increased, and as the exposure duration increased. Groundwater Cr and Pb were promptly attenuated by the sediments, the mobility of Cu was low and decreased rapidly as sediment pH increased above 4.5, while Cd, Ni and Zn were the most easily transported to the surface sediments and released to the overlying waters. For groundwaters of pH 3, metal migration velocities through sandy sediments were generally 0.5-2% (Cr, Pb), 1-6% (Cu) and 4-13% (Cd, Ni, Zn) of the total groundwater velocity (9-700 m/yr). The oxidative precipitation of Fe(II) and Mn(II) in the groundwaters did not affect metal mobility through the sediments. The results indicated that the efflux of acidic and metal-contaminated groundwater through estuarine sediments would affect organisms resident in sandy sediments more greatly than organisms resident in fine-grained, silty, sediments.     

Distribution and relationships of selected trace metals in molluscs and associated sediments from the Gulf of Aden, Yemen

Concentrations of Cd, Pb, Zn, Cu, Ni, Co, Cr, Mn and Fe in the soft tissue of Turbo coronatus, Acanthopleura haddoni, Ostrea cucullata and Pitar sp., as well as in associated surface sediments (bulk and bioavailable metal concentrations) from the Gulf of Aden, Yemen, were determined by atomic absorption spectrophotometry method. Large differences between size-classes of molluscs in metal concentrations were recorded. Significant spatial differences in metal concentrations in both the soft tissue of the molluscs and associated sediments studied were mostly identified. Statistically significant correlations (p<0.01) between concentrations of selected metals were observed. A slope of the linear regression is significantly higher than unity for Fe (9.91) and Cd (3.45) in A. haddoni and for Ni (4.15) in T. coronatus, suggesting that the bioavailability of these metals is disproportionally increased with a degree of enrichment of the sediments in Fe, Cd and Ni, respectively. A slope constant approximating to unity (1.14) for Cu in A. haddoni relative to its concentration in sediment extract implies that bioavailability of this metal proportionally increased with growing concentrations of its labile forms in the associated sediment. The degree of contamination of Gulf of Aden waters by the metals studied is discussed and the potential ability of molluscs, especially A. haddoni and T. coronatus, as biomonitors of metallic pollutants is postulated.     

Spatial variation of heavy metals in surface sediments of Hong Kong mangrove swamps

The degree of heavy metal contamination in the fine-grained (<63 microm) and sand-sized (2 mm-63 microm) fractions of surface sediments in 18 different mangrove swamps (144 random samples) in Hong Kong was examined. Higher concentrations of heavy metals were found in the fine-grained than the sand-sized fractions of the sediment; however, the differences between these two fractions became less significant when the swamp was more contaminated. The principal component analyses show that the 18 mangrove swamps, according to the median concentrations of total heavy metals, were clustered into four groups. The first group included three mangrove swamps in Deep Bay region which are seriously contaminated, with heavy metal concentrations in sediments around 80 microg g(-1) Cu, 240 microg g(-1) Zn, 40 microg g(-1) Cr, 30 microg g(-1) Ni, 3 microg g(-1) Cd and 80 microg g(-1) Pb. The second cluster, made up of another four swamps distributed in different geographical locations (two in Sai Kung district and two in Tolo region), also had elevated levels of Cu, Pb, Ni and Cr in the sediments. Field observation reveals that these seven stands received industrial, livestock and domestic sewage as well as pollution from mariculture activities, suggesting that anthropogenic input is the main source of heavy metal contamination in Hong Kong mangroves. The sediments from other mangrove swamps were relatively uncontaminated.     

Metal partitioning in river sediments measured by sequential extraction and biomimetic approaches

We quantified the concentrations and distributions of metals (Cd, Cr, Cu, Ni, Pb, and Zn) in the sediments of Tuen Mun River, Hong Kong. The potential bioavailability of metals was assessed with a biomimetic extraction method using the sipunculan gut juices. The sediments were characterized by relatively high concentrations of trace metals. Field collected sediments were highly anoxic and the ratio of simultaneously extractable metal (sigmaSEM) to acid volatile sulfide (AVS) was much less than one in these sediments. The majority (>67%) of Cd, Pb, and Zn were bound to AVS, thus their concentrations in the sediment porewater were low. In contrast, Ni was little bound to AVS due to its lower ratios of SEM-Ni to total Ni concentrations. For Cu, relatively high concentrations in the sediment porewater was found, and total organic carbon, AVS and other resistant sulfide phase were the controlling factors for sedimentary Cu partitioning. Net metal adsorption from gut juices to anoxic sediments was observed in metal extraction experiments, suggesting that AVS determined the bioaccumulation and potential bioavailability of most metals in these sediments. Extraction of metals from the oxidized sediments by the gut juices was mainly attributed to metal redistribution from AVS to other geochemical phases. The gut juices were the most effective solvent or extractant than the simple electrolyte solution [I (NaNO(3)) = 0.01 M] and the natural overlying water. Cd was more easily extracted from the oxidized sediments than Zn that tended to have a stronger binding affinity with Fe-Mn oxide, clay and organic matter. The application of partial removal techniques in metal extraction experiments further demonstrated the differential controls of various sediment geochemical phases in affecting metal bioavailability, with the order of TOC > Fe-Mn oxides > carbonate.     

The origin of speciation: trace metal kinetics over natural water/sediment interfaces and the consequences for bioaccumulation

The speciation of heavy metals was measured over a variety of natural and undisturbed water/sediment interfaces. Simultaneously, two benthic species (oligochaete Limnodrilus spp. and the midge Chironomus riparius) were exposed to these sediments. Under occurring redox conditions, free ion activities of trace metals Cd, Cu, Ni, Pb, and Zn were measured with a chelating exchange technique, while geochemical conditions (i.e., redox) remained in tact. Free ion activities were compared with total dissolved concentrations in pore waters and surface waters in order to relate speciation to bioaccumulation. Limnodrilus spp. and C. riparius have accumulation patterns that could be linked to time-dependent exposure concentrations, expressed as chemical speciation, in the surface water and the sediment's pore water. Concentrations of free metal ions in the overlying surface water, rather than in sediment pore water, proved to be the best predictor for uptake. For the first time, measurements are obtained from sediments without disturbing physical-chemical conditions and thus bioavailability, a major restriction of other studies so far.     

Assessing the cause of impacts on benthic organisms near Rouyn-Noranda, Quebec

Sediments from lakes near Rouyn-Noranda, Quebec, contain elevated concentrations of several metals, including Cd, Cu, Pb and Zn. Amphipods, fingernail clams, mayflies and tanytarsid midges were absent, and sediment toxicity was observed in chronic tests with Hyalella in sediments from Lac Dufault, the lake closest to Rouyn-Noranda. Bioaccumulation by Hyalella demonstrated elevated bioavailability of Cd, Co, Cr, Pb and Tl, but only Cd was accumulated to levels close to the toxic threshold. Copper, which is regulated by Hyalella, was not elevated in these amphipods, but it was elevated in overlying water in the toxicity tests. Toxic effects in Lac Dufault sediments are probably caused primarily by Cd, at least in amphipods, with a possible minor contribution from Cu. An integrated assessment, including sediment chemistry, benthic community composition, sediment toxicity, metal bioaccumulation in benthos, and comparison of bioaccumulation and/or overlying water concentrations with threshold effect concentrations, provides the best indication of effects and their cause.     

Occurrence of platinum and additional traffic related heavy metals in sediments and biota

Non-point sources play an important role in metal emissions into surface waters. One of the most important non-point sources is automobile traffic. Recent studies determining traffic related heavy metals in surface waters have concentrated mainly on worst case scenarios by analyzing heavy metal loads in waters and sediments close to storm-water overflow inlets. The present study aims at identifying traffic related heavy metals in moderately polluted sites, as they occur in highly urbanized regions. Therefore, the concentrations of eight traffic related metals (Pt, Sb, Mo, Cd, Pb, Cu, Cr and Zn) were determined in sediment and crustacean samples from eight different aquatic habitats in the Ruhr district, Germany. Traffic related heavy metals could be identified in sediment and biota samples as a combination of heavy metals (Pt, Sb, Cd, Pb for sediments and Pt and Sb for crustacean samples). Pt concentrations received special attention due to the relatively recent occurrence of anthropogenically emitted Pt in the environment. At six sampling sites, Pt was detected in sediment and/or biota samples. The uptake of Pt compared to other traffic related heavy metals by Asellus aquaticus and Gammarus pulex is relatively high and can be compared with the uptake rates of essential metals like Zn.     

Heavy metals from the River Adayar,India: infiltration into the adjacent groundwater aquifer

In the Adayar riverbed and its estuary 5 undisturbed sediment cores were drilled using a petrol-driven hammer. Cores of a depth of 4-5 m were sampled in 0.5 m steps. The distribution of heavy metals (Cr, Mn, Ni, Cu, Zn, Cd and Pb) in the top layers of fluvial and estuarine sediments indicates recent anthropogenic input: Revealing that the river acts as a sink for drainage from the residential and industrial zones. In this study, the mobilization of heavy metals into greater depths and their probable effects on the groundwater body are discussed. The high concentration of heavy metals and the influent character of the river Adayar allow the mobilization of metal ions and their transport into the deeper layers of the sediment. A changing environment due to effects such as saltwater intrusion and monsoon floods is the driving force for this phenomenon.     

Lac Dufault sediment core trace metal distribution, bioavailability and toxicity to Hyalella azteca

To determine changes in metal distribution, bioavailability and toxicity with sediment depth, two 20-cm-long replicate cores were collected from a lake historically subjected to the influence of metal mining and smelting activity. The vertical distribution of Pb, Cd and Cu in sediment was similar for all three metals, with the surface layers showing enrichment and the deeper (pre-industrial) layers showing lower concentrations. Toxicity of each sediment core section was determined in laboratory tests with the freshwater amphipod Hyalella azteca. Bioavailable metal in each sediment slice was estimated from metal concentrations in overlying water in these toxicity tests and, for Cd, also from metal bioaccumulation. The profile for Cd in tissue was comparable to Cd in sediment and overlying water, but relative Cd bioavailability from sediment increased with sediment depth. Survival increased with increasing sediment depth, suggesting that surface sediments were probably less or non-toxic before industrialization.     

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.