Evaluation of Heavy Metals Pollution Loadings in the Sediments of the Ave River Basin (Portugal)

Sediment samples from the Ave river basin were collected with the aim of determining metal total pollution contents. Cr, Cu, Fe, Mn, Pb, Zn and VM at 550 °C were determined. Some physico-chemical parameters were also quantified in water samples collected in the water column just above the sediments.

Metal contamination factors (CF) indicated that sediments were not contaminated with Cu and Pb, slightly with Zn and moderately with Cr.

For sediments with high metal pollution loadings, the original BCR (Community Bureau of Reference) metal speciation protocol was also applied. Speciation studies showed that chromium was mainly associated with the oxidisable plus residual fractions (>85%). These results suggest that changes in the physico-chemical properties of the river water (e.g. pH, Eh) should not be accompanied by a significative release of chromium from sediments.

The relationships between chromium speciation fractions, physic-chemical parameters of the sediments and water samples were studied by Principal Component Analysis, and allowed to reduce the dimensionality of the data matrix from 14 to 3 significant components accounting for 89% of the variance. It was found that hydrous Fe/Mn oxides and organic matter are the “carriers” of chromium associated to fractions exchangeable and oxidable.     

Characterization of Heavy Metal Fractions in Agricultural Soils by Sequential Extraction Procedure: The Relationship Between Soil Properties and Heavy Metal Fractions

The present research was conducted to determine heavy metals in agricultural soils from Çanakkale, Turkey, using a sequential extraction procedure (acid soluble, reducible, oxidizable, and residual) as proposed by the Community Bureau of Reference (BCR) of the European Commission. Soil samples were taken from 12 different cultivated sites and analyzed for Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn concentrations. The results revealed an order of Mn > Cd > Pb > Co > Ni > Cu > Zn > Cr for the heavy metals based on the sum of the first three fractions (acid soluble + reducible + oxidizable). The relationships between soil properties and each metal fraction were identified through Pearsons's correlation analysis. Hierarchical cluster analysis was performed to determine the behaviors and similarities of metals in each fraction. While Mn, Pb, and Zn exhibited subjective behaviors in the acid-soluble fraction, Cd, Co, Cu, Cr, and Ni exhibited similar behaviors with each other.     

Assessment of Heavy Metal Pollution in Water and Sediments from the Ghalechay River,Baychebagh Copper Mine Area,Iran

The concentrations of selected heavy metals in sediments and waters in Baychebagh copper mine were determined using ICP-OES. Except for Co, the average concentrations of Cd, Cu, Pb, and Zn in sediments from the Ghalechay River in the district exceed the world-average shale and continental upper crust value. Enrichment factors for Pb, Cu, and Cd were significantly enriched in sediments, indicating environmental contamination. Geoaccumulation index calculated for different sampling stations indicates that the sediments are unpolluted with respect to Co and Zn while unpolluted to moderately polluted with Cu and highly polluted with Pb and Cd. The Sediment Quality Guidelines (SQGs) suggest that Cd and Pb may pose the highest risk for the environment. Sequential extraction analyses of sediments revealed that Cu, Co, Pb, and Zn bound to extractable, carbonate, reducible and oxidizable fractions are lower than residual fraction. About 10% of the total Pb was associated with the exchangeable fraction, indicating remobilization, while Cd (89%), Pb (73%) Co (58%), Cu (76%), and Zn (68%) closely associated with the residual and oxidizable fractions, resulting in their environmental immobility. The residual forms are not expected to be released under normal conditions in the river and could be considered an inert phase.     

Heavy Metal Partitioning in Bottom Sediments of the Matanza-Riachuelo River and Main Tributary Streams

This study provides geochemical partitioning, potential bioavailability, and enrichment of Cd, Cu, Pb, and Zn in bottom sediments collected from the Matanza-Riachuelo River and its main tributary streams. A modified Tessier sequential extraction procedure, complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, was applied to determine the partitioning of metals into four fractions (metals bound to amorphous sulfide, carbonate, and exchangeable), bound to Fe/Mn oxides (reducible), bound to organic matter/sulfide (oxidizable) and residual. Spatial and vertical distributions of metals were studied. The core sediments show a decreasing concentration of metals with depth. In top sediments, non-residual Cu was mainly associated with oxidizable phase, whereas Pb, Cd, and Zn were mainly associated with amorphous sulfide. Pb exhibited the highest enrichment in all sites. The ratio AVS/SEM was greater than one at sediment sections close to the water column, indicating that metals extracted with hydrochloric acid were mainly associated with the amorphous sulfide. The strong influence of amorphous sulfide in the retention of Cd, Pb, and Zn in anoxic sediments of Matanza-Riachuelo river system suggests that dredging and aeration could lead to the remobilization of metals from sediments to the water column, hence making the metals more available to the biota.     

Trace Metal Bioaccumulation in Epibenthic Macroinvertebrates (EMI) from the San Pedro Shelf,California

Trace metal/metalloid (As, Ag, Cd, Cr, Cu, Hg, Ni, Pb, Se, Zn) bioaccumulation was measured over a period of ten years (1985–1995) in five species of epibenthic macroinvertebrates (EMI) from the San Pedro Shelf, California. Four of the species are numerical dominants in the Southern California Bight (SCB) and two species are commercially harvested. Among three echinoderms, a predatory sea star yielded highest tissue concentrations compared to a sea cucumber and a sea urchin, and concentrations measured in a mantid shrimp exceeded those from a prawn. Comparison of trace metal bioaccumulation from the study area, including the ocean outfall, and elsewhere indicated that bioaccumulation in local EMI was generally low. Measurements from an outfall station and two reference stations were used to evaluate the spatial and temporal relationship between trace metal bioaccumulation and the wastewater discharge. It was concluded that there was no spatial or temporal relationship between EMI trace metal bioaccumulation and the discharge.     

Fractionation of metals in the Sa1/2 sediment core from Lake Sarbsko (northern Poland) and its palaeolimnological implications

Abstract

This article documents and interprets stratigraphical changes in fractionation of Fe, Mn, Mg, K, Pb, Cu and Zn in the Sa1/2 sediment core from a coastal freshwater lake, Lake Sarbsko (northern Poland). The elements were sequentially extracted from the samples to distinguish five geochemical fractions: exchangeable, acid-extractable, reducible, oxidisable and residual. The analyses revealed substantial variations in geochemical partitioning of the elements and showed no correlation between the fractionation patterns and lithology of the sediments. In the sediments of Lake Sarbsko, iron is mainly bound to sulfides. Potassium occurs in its residual form. Magnesium and zinc are associated with carbonates and aluminosilicates, while copper occurs in compounds with organic matter and sulfides. Lead is found in connection with aluminosilicates and, to a lesser extent, with sulfides and organic matter. Manganese is partitioned between the oxidisable, acid-extractable, and exchangeable fractions. Heavy metals and potassium display the overall tendency to reduce the contents of their residual forms towards the top of the depositional sequence. Fe, Mn, Mg and Zn were found to be the most susceptible to post-sedimentary mobilisation.     

Ecotoxicological Risk Assessment of Polychlorinated Biphenyls (PCBs) in Bank Sediments from along the Yamuna River in Delhi,India

The River Yamuna originates from the Yamunotri glacier of the Himalayas and travels 22 km in the Delhi region. The river is used for various purposes in Delhi including drinking water supply. Twenty-eight polychlorinated biphenyls (PCBs) congeners were measured in bank sediments along the river, and their ecotoxicological risk was evaluated. Concentrations of ∑28PCBs varied from 0.20–21.16 ng g^?1 (dry wt.) with mean and median values of 6.63 ng g^?1 and 5.84 ng g^?1 (±0.69 ng g^?1), respectively. The concentration of 12 dl-PCBs concentrations varied from 0.04–2.86 ng g^?1 with a mean of 1.04 ± 0.11 ng g^?1, and their toxic equivalency ranged between <0.01–28.67 pg WHO-TEQ g^?1 with a mean of 10.77 ± 1.06 pg WHO-TEQ g^?1. CB-37, CB-44, CB-114, and CB-118 congeners were dominant among all PCBs congeners. The tri-PCBs (49%) were the main contributors to the PCB homolog followed by tetra-PCBs (35%), and penta-PCB (14%). Because there are no environmental guidelines in India for PCBs in river and marine sediments, concentrations of PCBs and their toxic equivalents were compared in a screening-level assessment with established freshwater sediment quality guidelines and found lower than those guideline values, which suggests no adverse ecotoxicological effect.     

Fabrication of a Dipole-assisted Solid Phase Extraction Microchip for Trace Metal Analysis in Water Samples

This paper describes a fabrication protocol for a dipole-assisted solid phase extraction (SPE) microchip available for trace metal analysis in water samples. A brief overview of the evolution of chip-based SPE techniques is provided. This is followed by an introduction to specific polymeric materials and their role in SPE. To develop an innovative dipole-assisted SPE technique, a chlorine (Cl)-containing SPE functionality was implanted into a poly(methyl methacrylate) (PMMA) microchip. Herein, diverse analytical techniques including contact angle analysis, Raman spectroscopic analysis, and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis were employed to validate the utility of the implantation protocol of the C-Cl moieties on the PMMA. The analytical results of the X-ray absorption near-edge structure (XANES) analysis also demonstrated the feasibility of the Cl-containing PMMA used as an extraction medium by virtue of the dipole-ion interactions between the highly electronegative C-Cl moieties and the positively charged metal ions.     

Total concentrations and fractionation of heavy metals in road-deposited sediments collected from different land use zones in a large city (Nanjing), China

Abstract

In order to investigate heavy metal contamination in an urban environment during urbanization and economic development, 35 road-deposited sediment samples were collected from seven different land-use zones (commercial, residential, traffic, scenic park, educational, industrial and peri-urban) in Nanjing, a large city in P.R. China. The ranges of total metal concentrations found were: 28.7–272 mg kg^?1 for Cu; 24.8–268 mg kg^?1 for Ni; 37.3–204 mg kg^?1 for Pb; 140–798 mg kg^?1 for Zn; 0.44–2.19mg kg^?1 for Cd; and 60.6–250 mg kg^?1 for Cr. Metal fractionation was carried out using a modified three-step European Bureau of References (BCR) sequential extraction procedure. Cadmium and Zn were found predominantly associated with the acid extractable fractions; Ni and Cr were dominant in the residual fraction; Pb was predominantly associated with the residual and reducible fractions; Cu was dominant in the oxidizable and residual metal fractions. Based on the sum of the acid-extractable, reducible, and oxidizable fractions, Cd, Zn and Pb are potentially the most toxic metals in the road-deposited sediment in Nanjing. No significant differences, except for Zn, were found in the metal fractionation pattern for Cu, Ni, Pb, Cd, and Cr in different land use zones.     

Fractionation and ecological risk assessment of trace metals in surface sediment from the Huaihe River,Anhui, China

Abstract

The Huaihe River has suffered increasing pressure from pollutants including metals from anthropogenic activities. In this study, enrichment and fractionation behavior of trace metals were analyzed in sediment samples obtained from fish spawning area of the Huaihe River (Anhui Section) to evaluate the potential ecological risk of trace metals to aquatic organisms. Geochemical indices including enrichment factor and geo-accumulation index as well as mean probable effect concentration quotient and risk assessment code were adopted to assess the contamination degree and potential ecological toxicity. Results showed that the total contents of Cu, Pb, Zn, Cr, Cd, As, and Hg in sediment were 23.1?±?6.4, 32.3?±?11.1, 76.8?±?14.2, 84.6?±?17.2, 0.2?±?0.1, 9.0?±?3.0, and 0.031?±?0.010?mg/kg, respectively. The indexes EF and I_geo revealed slight accumulation for Pb, Zn, Cr, Cd, and As in some sampling sites. The result of Q_m-PEC demonstrated that trace metals in sediment were not toxic to aquatic organisms. Most trace metals appeared to mainly associate with the residual form suggesting lower mobility whereas Cd presented a relative higher exchangeable fraction indicating a great degree of bioavailability. The result of risk assessment code (RAC) evaluation revealed that Cd poses a medium ecological risk for aquatic organisms whereas most of the other trace metals pose low risks.     

Trace Metal Concentrations in Marsh Profiles Under the Influence of an Emerging Delta (Atchafalaya River and Wax Lake Delta) Overlying a Several Thousand Year Old (Former)Mississippi River Delta Lobe

There are concerns over the increasing concentrations of trace metals being found in the environment. Deltas are essentially integrators of watershed contamination as they are the repositories of sediment transported from and through the watershed. In order to assess changes in trace metal concentrations transported by the Mississippi River–Atchafalaya River systems, vibracores were collected from three coastal freshwater marsh sites under the influence of the Atchafalaya River and emerging Wax Lake Delta (WLD). The cores extended to a depth of 4 m which included deposits of an earlier Mississippi River Delta lobe. C-14 dating showed an age at the lower depth corresponding to approximately 3500 years ago. Vertical profile distribution of metals and metalloids were measured and comparisons between older deposits and concentrations in recent deposits were made. Concentrations of As, Cr, Cu, Ni, Zn, Mo, V, Co, and Hg metals were measured in the profiles along with Fe, Mn, and Al. There was no significant increase in heavy metals or metalloids in recent years as compared to more than 3000-year-old sediment associated with an earlier Mississippi River Delta lobe. Results show that sediment diversion through the Wax Lake Outlet did not increase concentrations of these metals in surface marsh soils. The metal concentrations in the marsh profile were compared to ERL (effects range low) and ERM (effects range medium) values to allow an ecotoxicological assessment. Arsenic was below the ERM values but was greater than the ERL which indicate a potential toxicity under certain conditions. All other metal/metalloids measured were below ERL limits. This study suggests that planned Mississippi River sediment diversions designed to slow the rate of coastal land loss are not likely to lead to trace metals contamination.     

Fractional phosphate composition in sediments from a tropical river (Catatumbo River, Venezuela)

The distribution of phosphate species in the Catatumbo River, Venezuela, was studied using a sequential extraction scheme. Extraction was performed using 1.0 M NH₄Cl, 0.1 M Na₂S₂O₄–NaHCO₃, 1.0 M NaOH and 0.5 M HCl. Total phosphate was in the range between 121 and 581 g g^–1 D.W. About 64% of the total phosphate is inorganic and present the following composition: 1% NH₄Cl-P, 10% BD-P, 20% NaOH-P, 33% HCl-P; while org-P is 36%. The main form of P in sediment from the Catatumbo River is calcium bound-P, like apatite. The metal concentrations present in sediment are in the following order: Fe> Al > Ca > Mg > Mn. Relationships between P and Fe, Al and Ca were found. Cluster analysis showed that speciation is not dependent on the inorganic matrix of the sediments. Analysing the influence of NaOH concentration and duration of the extraction invalidated the use of NaOH as extracting agent in P-speciation.     

Trace Element (Pb,Cd, and As) Contamination in the Sediments and Organisms in Zhalong Wetland,Northeastern China

This study examined Tessier's fractions of Pb, Cd, and As in the sediments and their potential toxic effects on four aquatic animals, i.e., Enchytraeus of Lumbricidae, Cipangopaludina chinensis of Viviparidae, Cybister japonicus Sharp of Dytiscidae, and Perccottus glenii Dybowski of Odontobutidae in Zhalong Wetland, Northeastern China. Results show that Cd poses a high risk to the biota in Zhalong Wetland. The geo-accumulation indices indicate that the region only has background concentrations of As, although it is slightly polluted by Pb and is seriously polluted by Cd. The exchangeable fraction receives minor contributions from these metals: 0.8% for Pb, 2.8% for Cd, and 4% for As. Three reed organs and four aquatic animal groups contain detectable concentrations of Pb, Cd, and As, with the following order of increasing concentrations: stem < rhizome < root < Viviparidae < Odontobutidae < Dytiscidae < Lumbricidae. Relatively low bioaccumulation factor (BAF) of As occurred in four aquatic organisms, whereas significantly higher BAFs of Pb and Cd were found in the earthworm than other aquatic organisms (P < 0.05). The earthworms (Enchytraeus of Lumbricidae) were recommended to be used as a suitable indicator for Pb, Cd, and As toxic risk level in this region.     

Heavy Metals (Cd,Cu, Ni,Pb, and Zn) Fractionation in River Sediments,Hamedan, Western Iran

Five heavy metals (Cd, Cu, Ni, Pb, and Zn) in river sediments from Abshineh River, Hamedan, western Iran, were fractionated by a sequential extraction procedure. Cu, Ni, Pb, and Zn existed in sediments mainly in residual fraction (mean 92%, 86%, 77%, and 65%, respectively), whereas Cd occurred mostly as organic matter (mean 41%) and exchangeable (mean 25%) fractions. The mean percent of mobile fraction of Cd, Cu, Ni, Pb, and Zn in contaminated sediments was 25, 13, 4, 24, and 10, respectively, which suggests that the mobility and bioavailability of the five metals in sediments probably decline in the following order: Cd = Pb > Cu > Zn > Ni. The metal levels were also evaluated according to the contamination factor, which revealed significant anthropogenic pollution of Cd and Pb.     

Impacts of Yellow River Irrigation Practices on Trace Metals in Surface Water: A Case Study of the Henan-Liaocheng Irrigation Area,China

Large-scale irrigation practices may disturb local hydrologic cycles and distribute trace metals throughout the environment. Reported here is the spatial pattern of trace metals and associated health risks in an agricultural area of China, which has a long history of irrigation with water from the Yellow River. Multivariate statistical analyses and a risk-assessment model were employed to interpret the environmental data. It indicated that Zn, Se, B, Ba, Fe, Mn, Mo, Ni, V, Al, Li, Sr, Be, Cd, Cr, Cu, and Pb were all detected in the surface waters. Compared to drinking water guidelines, the primary trace metal pollution components (Al, Fe, Se, B, Mn, and Zn) exceeded drinking water standards by 40.7%, 14.8%, 29.6%, 25.9%, 11.1%, and 14.8%, respectively. Except for one site that exhibited anomalous metal concentrations, landscape features of trace metals identified a uniform distribution of trace metals for all sample sites. The calculated mean value of Hazard Quotients (HQs) exceeded the USEPA's recommendations by a factor of 2.9 times the threshold value. Primary sources of trace metals were associated with natural deposition, industrial and agrochemical processes, and a mixed source of both geogenic and anthropogenic origins.     

Heavy Metal Concentration in Sediments of the Nhue River and its Water-Irrigated Farmland Soil in the Suburbs of Hanoi,Vietnam

The heavy metal pollution of sediment in the Nhue River, which receives wastewater from the To Lich and Kim Nguu River system, was investigated together with the effects of use of this water for irrigation of the surrounding farmland. Eighty soil samples and 40 sediment samples were collected from six locations in the Nhue River and two locations in the To Lich River for chemical and physical analyses. The results showed that the sediments in the Nhue River are heavily polluted by metals (71–420 mg/kg for Cu, 77–433 mg/kg for Pb, 150–350 mg/kg for Zn, 0.7–8.7 mg/kg for Cd, 80– 583 mg/kg for Cr, and 32–70 mg/kg for Ni). There were positive correlations between heavy metal concentration and both clay and organic matter contents in the sediment samples. The concentrations of all metals in soil samples were much higher than the background levels in the farmland, Cd, Cu, and Pb, exceeding Vietnamese standards for agricultural grounds.     

Sequential extractions of inorganic and org-Phosphate from fish pond sediments (Deroua station,Beni Mellal,Morocco) by different fractionation methods

The carp ponds of Deroua station (Beni Mellal, Centre of Morocco) receive a large quantity of fertilizers, particularly urea and triple super phosphate during the entire period of culture. Only a small part of that is necessary to promote an adequate development of phytoplankton, the base of the food chain. A large part of the phosphate added to the ponds is stocked in pond soils and can be released under specific conditions. Although some phosphate is necessary for the development of aquatic populations, too large of an input causes problems. Therefore, knowledge of the external load and the mobility of the internal pool is essential for the purpose of management against eutrophication. In order to assess the inorganic and organic fractions of phosphate present in sediments, different methods of P fractionation were compared. The methods do not give the same results. In the Deroua sediments, calcium-bound phosphate represents the major part of total phosphate between 86% and 91% according to the different methods. The org-Phosphate represents a small part and varies considerably depending on the different methods between 0.87 and 5%. EDTA extractions (Golterman, 1996) have an advantage over other methods such as the Sedex, the Hieltjes &; Lijklema and the Bonzongo procedures.     

Collembola in the Bed Sediments of an Alpine Gravel Stream (RITRODAT-Lunz Study Area,Austria)

In the creek “Oberer Seebach”, 355 springtails belonging to 42 species were collected from the water-filled pore space of the bed gravel proper and the adjacent bank sediment. Almost 10 % of 2094 samples contained Collembola, with a mean density of 1.8 specimens per positive sample. The topographic distribution of the most abundant species Lepidocyrtus lignorum, Agrenia bidenticulata, and Folsomia quadrioculata suggests that riparian and eurytopic forms are frequently washed into the channel and transported down to a considerable sediment depth without injury to the animals. The rising groundwater table in the bank sediment traps no riparian, but predominantly hemiedaphic species. Euedaphic springtails are rare, especially in the groundwater samples.     

Evaluation and Potential Health Hazard of Selected Metals in Water,Sediments, and Fish from the Gomti River

The health hazard associated with the consumption of fish from the Gomti River in India, contaminated with the heavy metals Cr, Cu, Mn, Ni, Pb, and Zn was assessed in terms of target hazard quotients (THQs). The concentrations of metals (mg kg^?1, wet weight basis) in the muscle tissues of different fish species Mastacembelus puncalus, Clupisona garua, Cyrinous carpio, Botia lochachata, Channa punctatus, Heteropneustise fossilis, Puntius sofore, and Clarious batrachus ranged as follows: Cr (2.2–21.4), Cu (0.3–14.3), Mn (2.3–5.5), Ni (0.5–10.9), Pb (1.0–3.9), and Zn (12.3–46.9). The accumulation of metals in fish muscle tissue was in the order: Zn > Cr > Ni > Mn > Cu > Pb. THQs indicated a potential health hazard to children due to the consumption of fish contaminated with Ni and Pb; their THQs were greater than 1 for almost all fish species except for Ni in C. garua (THQ, 0.07) and C. carpio (THQ, 0.90). For adults, insignificant health hazard was associated with THQs less than 1 for all metals in the different fish species, but long-term exposure to these metals and subsequent bioaccumulation in the body may require additional investigation.     

Seasonal and spatial variations of heavy metals in surface sediments collected from the Baoxiang River in the Dianchi Watershed,China

To explore potential ecological hazards due to heavy metals in the Dianchi Lake Watershed, a three-stage European Community Bureau of Reference (BCR) sequential extraction procedure was applied to examine the spatial distributions and relative speciation ratios of Zn, Cu, Ni, Pb, and Cr in Baoxiang River sediments during wet and dry seasons. The metal species have similar spatial variations during different seasons. In the upstream reaches of the Baoxiang River, heavy metals reside primarily in the non-extractable residual fraction (72–90%). In the midstream, the residual fraction (35–89%) remains dominant, but the extractable fraction increases, featuring especially notable increases in the reducible fraction (5–40%). Downstream, the Cu, Ni, Pb, and Cr residual fractions remain high (46–80%) and the extractable fractions increase rapidly; the Zn extractable fraction is quite high (65.5%). Anthropogenic sources drive changes in heavy metal speciation. Changes in the river environment, such as pH and oxidation-reduction potential, also affect speciation. The reducible fraction of heavy metals in Baoxiang River sediments is most sensitive to pH. Potential ecological risk assessments for these five elements indicate that risks from Zn and Pb are mild to moderate in the middle and lower reaches of the river.