Prioritisation of organic contaminants in a river basin using chemical analyses and bioassays

Region-specific contaminant prioritisation is an important prerequisite for sustainable and cost-effective monitoring due to the high number of different contaminants that may be present. Surface water and sediment samples from the Sava River, Croatia, were collected at four locations covering a 150-km-long river section characterised by well-defined pollution gradients. Analysis of contaminant profiles along the pollution gradients was performed by combining toxicity screening using a battery of small-scale or in vitro bioassays, which covered different modes of action, with detailed chemical characterisation based on gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). A large number of contaminants, belonging to different toxicant classes, were identified in both analysed matrices. Analyses of water samples showed that contaminants having polar character occurred in the highest concentrations, while in sediments, contributions from both non-polar and amphiphilic contaminants should be taken into account. Estimated contributions of individual contaminant classes to the overall toxicity indicated that, besides the classical pollutants, a number of emerging contaminants, including surfactants, pharmaceuticals, personal care products and plasticizers, should be taken into consideration in future monitoring activities. This work demonstrates the importance of the integrated chemical and bioanalytical approach for a systematic region-specific pollutant prioritisation. Finally, the results presented in this study confirm that hazard assessment in complex environmental matrices should be directed towards identification of key pollutants, rather than focusing on a priori selected contaminants alone.     

Limitations of reverse polyethylene samplers (RePES) for evaluating toxicity of field contaminated sediments

Passive samplers are used to measure dissolved nonionic organic contaminants (NOCs) in environmental media. More recently, reverse polyethylene samplers (RePES) have been used with spiked sediments to recreate interstitial water exposure concentrations and observed toxicity. In the present study, RePES were used with field contaminated sediments. The RePES was not capable of recreating the pattern of toxicity with the amphipod and mysid observed with intact field sediments. Decreased survival in the RePES exposures as compared to the whole sediment exposures was most likely caused by an overexposure to NOCs due to a lack of surrogate black carbon in the RePES system. As an alternative, aqueous phase studies were performed in which polyethylene was allowed to equilibrate with slurries of intact sediments for 3 weeks. Three weeks was found to be an insufficient amount of time for the polyethylene to equilibrate with the sediment. An additional study demonstrated 3 months was sufficient for lower contaminant concentrations, but might not be an adequate amount of time for more highly contaminated sediments. The aqueous phase transfer approach may be useful if equilibration is sufficiently long, although this length of time may be impractical for use in certain applications, such as toxicity identification evaluations (TIEs).     

Sulfamethoxazole sorption by sediment fractions in comparison to pyrene and bisphenol A

The environmental behavior of antibiotics has attracted great research attention. However, their sorption mechanisms in soils/sediments are still unknown. Comparison of the sorption properties between the widely-studied hydrophobic organic contaminants (HOCs) and antibiotics may provide valuable insight to antibiotic sorption mechanisms. Thus, in this study batch experiments for pyrene (PYR), bisphenol A (BPA), and sulfamethoxazole (SMX) sorption were conducted on a sediment sample and its separated fractions. Our results showed the high sorption of PYR on black carbon and organic matter. Although high sorption of SMX was observed for both separated organic fractions (humic acids) and inorganic mineral particles, the original sediment particles showed relatively low sorption. Competitive sorption between SMX and dissolved humic acid on mineral particles was observed in this study. This competitive interaction is a unique process for antibiotic sorption in soils/sediments compared with apolar HOCs and may be one of the important factors controlling the antibiotic sorption.     

Adverse effects of fullerenes (nC60) spiked to sediments on Lumbriculus variegatus (Oligochaeta)

Effects of fullerene-spiked sediment on a benthic organism, Lumbriculus variegatus (Oligochaeta), were investigated. Survival, growth, reproduction, and feeding rates were measured to assess possible adverse effects of fullerene agglomerates produced by water stirring and then spiked to a natural sediment. L. variegatus were exposed to 10 and 50 mg fullerenes/kg sediment dry mass for 28 d. These concentrations did not impact worm survival or reproduction compared to the control. Feeding activities were slightly decreased for both concentrations indicating fullerenes’ disruptive effect on feeding. Depuration efficiency decreased in the high concentration only. Electron and light microscopy and extraction of the worm fecal pellets revealed fullerene agglomerates in the gut tract but not absorption into gut epithelial cells. Micrographs also indicated that 16% of the epidermal cuticle fibers of the worms were not present in the 50 mg/kg exposures, which may make worms susceptible to other contaminants.     

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.     

Accelerated delivery of polychlorinated biphenyls (PCBs) in recent sediments near a large seabird colony in Arctic Canada

Polychlorinated biphenyls (PCBs) were measured in sediment cores from ponds located near a large seabird colony at Cape Vera, Devon Island, Arctic Canada. Surface sediment PCB concentrations were ∼5× greater in seabird-affected sites relative to a nearby control pond and were correlated with independent indicators of seabird activity including, sedimentary δ¹⁵N and lakewater chlorophyll a and cadmium concentrations. PCB fluxes were amongst the highest recorded from the High Arctic, ranging from 290 to 2400 ng m⁻² yr⁻¹. Despite a widespread ban of PCBs in the mid-1970s, PCB accumulation rates in our cores increased, with the highest values recorded in the most recent sediments. Possible mechanisms for the recent PCB increases include a vertical flux step driven by seabird-delivered nutrients and/or delayed loading of PCBs from the catchment into the ponds. The high PCB levels recorded in the seabird-affected sites suggest that seabird colonies are exposing coastal ecosystems to elevated levels of contaminants.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Pharmaceutical residues in tidal surface sediments of three rivers in southeastern China at detectable and measurable levels

Pharmaceutical compounds were increasingly detected in environmental matrices but little is known whether these compounds would transport to coastal zones via watersheds. Three typical tidal rivers in southeastern China were selected and 15 surface sediment samples (0–10 cm) were collected along a 50-km tidal section of each river. Surface sediment samples were frozen-drying and then extracted for pharmaceutical compounds by an accelerated solvent extraction system. The pharmaceutical compounds in extracts were scanned using a high-performance liquid chromatography/tandern mass spectrometry (HPLC-MS/MS). Three hundred and thirty compounds from nine pharmaceutical groups were detected with signal-to-noise above three (detectable level) in the surface sediments, of which 186 compounds were with a signal-to-noise above ten (measurable level). Of all, 291 and 80 compounds were detectable and measurable in all the three rivers, respectively. The Jiulong River showed a high load of pharmaceutical compounds in surface sediment than other two rivers. Of the nine pharmaceutical groups, the antihistamines and detoxification group and anti-infective drug group contributed five dominant compounds in the surface sediments in all the three rivers. Natures of pharmaceutical compounds rather than the sediment properties (pH, EC, and total carbon content) might influence their residues. The incredible number and intensity of pharmaceutical residues were detected in tidal surface sediments of the three rivers indicating that the pharmaceutical contamination should be strongly considered in China. Source identification and eco-toxicity assessment should be taken into account in the future study. Therapeutic medicine managements need to be strictly improved at a watershed scale to reduce loads of pharmaceuticals into aquatic ecosystems.     

GC × GC—A New Analytical Tool For Environmental Forensics

Comprehensive two-dimensional gas chromatography, GC × GC, is a new analytical tool with a tremendous capability to separate and identify organic compounds in complex environmental samples. GC × GC uses two different chromatography columns coupled serially by a modulator to produce a volatility by polarity separation and distribute compound peaks across a two-dimensional retention time plane. The two-dimensional separation produces an order of magnitude more resolved peaks than traditional GC methods. The grouping or ordering of the peaks in the GC × GC chromatogram facilitates the identification of unknown compounds and the comparison of complex environmental samples. When a mass spectrometer detector is used, each resolved GC × GC peak yields a single-component, interference-free mass spectrum that leads to accurate matching with mass spectral libraries. GC × GC examination of marine sediment extracts identified a wide variety of chemical contaminants including polychlorinated biphenyls, p -nonylphenol isomers, polycyclic aromatic hydrocarbons, benzotriazoles, and the alkane, cycloalkane, alkylbenzene, alkylnaphthalene, and biomarker fractions of petroleum. The two-dimensional GC × GC chromatogram image permits rapid screening of the sediment extracts for these and other unknown contaminants.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: Environmental legacy after twelve years of the Gulf war oil spill

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU_FCV,43). Samples were assigned to risk categories according to ESBTU_FCV,43 values: no-risk (≤1), low (>1-≤2), low-medium (>2-≤3), medium (>3-≤5) and high-risk (>5). Sixty seven percent of samples had ESBTU_FCV,43 > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30-<60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War.     

Effects of sediment quality on macroinvertebrates in the Sunraysia region of the Murray-Darling Rivers, Australia

A field-based microcosm approach was tested to identify deterioration of sediment quality in waterways using freshwater macroinvertebrates. The method can potentially identify the nature of contaminants based on species-specific responses. Sediments were collected from the Murray and Darling Rivers and irrigation drains within the Sunraysia region of south-eastern Australia and compared to non-polluted reference sediment. Clean sediments were also spiked with fertiliser to test whether nutrients affected the aquatic fauna. Seven of the eight sediments from the Sunraysia region had a negative impact on the macroinvertebrates, in particular sediment from the Darling River, which supported an impoverished fauna. Three species of chironomid showed varied responses to sediment quality and, although it was hypothesised that nutrients may have impacted on the macroinvertebrate fauna, the results suggest that other pollutants are also involved. The field-based microcosm method proved effective for determining the impact of sediment quality on indigenous macroinvertebrates.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Particle-size-fractioned transfer of dioxins from sediments to water columns by resuspension process

Particle-size-fractioned transfer of dioxins from sediments to water columns by resuspension process was investigated, using supernatant samples obtained from shaking experiments of sediment-water pairs simulating natural disturbances. The concentrations (dry-matter mass basis) of individual compounds (Cfraction) in two particle size fractions (0.1-1 and 1-10 μm) in the supernatants were generally slightly higher than those in the original sediment (Csed). Cfraction/Csed ratios ranged from 0.45 to 5.9 (median 1.5) without consistent differences among congener groups or consistent correlations against the number of chlorine atoms. The dioxin concentrations in the water column associated with the remaining sediment particles can therefore be estimated by those in the original sediment and by the concentration of suspended sediment particles in the water. The concentration of each compound in the remaining sediment particles (mostly 0.1-10 μm in size) can be roughly estimated by multiplying the concentration in the original sediment by 1.5.     

How are macroinvertebrates of slow flowing lotic systems directly affected by suspended and deposited sediments?

The effects of suspended and deposited sediments on the macroinvertebrates are well documented in upland streams but not in slower flowing lowland rivers. Using species found in lowland lotic environments, we experimentally evaluate mechanisms for sediments to affect macroinvertebrates, and in one experiment whether salinity alters the effect of suspended sediments. Suspended kaolin clay reduced feeding of Ischnura heterosticta (Odonata: Coenagrionidae) at high turbidity (1000-1500 NTU) but had no effects on feeding of Hemianax papuensis (Odonata: Aeshnidae) and Micronecta australiensis (Hemiptera: Corixidae). In freshwater (0.1 mS/cm), survival of Ischnura aurora was poor in clear water, but improved with suspended kaolin. Growth and feeding of I. aurora were unaffected by suspended sediments and salinity. Burial (1-5 mm) of eggs with kaolin or sand reduced hatching in Physa acuta (Gastropoda: Physidae), Gyraulus tasmanica (Gastropoda: Planorbidae) and Chironomus cloacalis (Diptera: Chironomidae). Settling sediments may pose greater risk to lowland lotic invertebrates than suspended sediments.     

Effects of black carbon on bioturbation-induced benthic fluxes of polychlorinated biphenyls

It is unknown whether carbonaceous geosorbents, such as black carbon (BC) affect bioturbation by benthic invertebrates, thereby possibly affecting sediment-water exchange of sediment-bound contaminants. Here, we assess the effects of oil soot on polychlorinated biphenyl (PCB) mass transfer from sediment to overlying water, for sediments with and without tubificid oligochaeta as bioturbators. PCB levels were so low that toxicity to the oligochaeta played no role, whereas soot levels and binding affinity of PCBs to soot were so low that pore water PCB concentrations were not significantly affected by binding of PCBs to soot. This setup left direct effects of BC on bioturbation activity as the only explanation for any observed effects on mass transfer. Mass transfer coefficients (K_L) for benthic boundary layer transport were measured by a novel flux method using Empore™ disks as a sink for PCBs in the overlying water. For the PCBs studied (logK_ow 5.2-8.2), K_L values ranged from 0.2 to 2 cm × d⁻¹ in systems without tubificids. Systems with tubificids showed K_L values that were a factor of 10-25 higher. However, in the presence of oil soot, tubificids did not cause an increase in mass transfer coefficients. This suggests that at BC levels as encountered under field conditions, the mechanism for reduction of sediment-water transfer of contaminants may be twofold: (a) reduced mass transfer due to strong binding of the contaminants to BC, and (b) reduced mass transfer of contaminants due to a decrease in bioturbation activity.     

Efficient degradation of organic pollutants with ferrous hydroxide colloids as heterogeneous Fenton-like activator of hydrogen peroxide

The capacity of a full-scale reclamation pond-constructed wetland (CW) system to eliminate 27 emerging contaminants (i.e. pharmaceuticals, sunscreen compounds, fragrances, antiseptics, fire retardants, pesticides, and plasticizers) and the seasonal occurrence of these contaminants is studied. The compounds with the highest concentrations in the secondary effluent are diclofenac, caffeine, ketoprofen, and carbamazepine. The results show that the constructed wetland (61%) removes emerging contaminants significantly more efficiently than the pond (51%), presumably due to the presence of plants (Phragmites and Thypa) as well as the higher hydraulic residence time (HRT) in the CW. A greater seasonal trend to the efficient removal of these compounds is observed in the pond than in the CW. The overall mass removal efficiency of each individual compound ranged from 27% to 93% (71% on average), which is comparable to reported data in advanced treatments (photo-fenton and membrane filtration). The seasonal average content of emerging contaminants in the river water (2488 ng L⁻¹) next to the water reclamation plant is found to be higher than the content in the final reclaimed water (1490 ng L⁻¹), suggesting that the chemical quality of the reclaimed water is better than available surface waters.     

Testing sediment biological effects with the freshwater amphipod Hyalella azteca: the gap between laboratory and nature

The freshwater amphipod, Hyalella azteca, is widely used in laboratory sediment toxicity and bioaccumulation tests. However, its responses in the laboratory are probably very different from those in the field. A review of the literature indicates that in its natural habitat this species complex is primarily epibenthic, derives little nutrition from the sediments, and responds primarily to contaminants in the overlying water column (including water and food), not sediment or porewater. In laboratory sediment toxicity tests H. azteca is deprived of natural food sources such as algal communities on or above the sediments, and is subjected to constant light without any cover except that afforded by burial into the sediments. Under these constraining laboratory conditions, H. azteca has been reported to respond to sediment or porewater contamination. In nature, contamination of overlying water from sediment is less likely than in the laboratory because of the large, generally non-static sink of natural surface water. H. azteca does not appear to be the most appropriate test species for direct assessments of the bioavailability and toxicity of sediment contaminants, though it is probably appropriate for testing the toxicity of surface waters. Toxic and non-toxic responses will be highly conservative, though the latter are probably the most persuasive given the exposure constraints. Thus H. azteca is probably a suitable surrogate species for determining sediments that are likely not toxic to field populations; however, it is not suitable for determining sediments that are likely toxic to field populations.     

Inconsistency and comprehensiveness of risk assessments for heavy metals in urban surface sediments

Numerous indices have been developed to assess environmental risk of heavy metals in surface sediments, including the total content based geoaccumulation index (I_geo), exchangeable fraction based risk assessment code (RAC), and biological toxicity test based sediment quality guidelines (SQGs). In this study, the three indices were applied to freshwater surface sediments from 10 sections along an urbanization gradient of the Grand Canal, China to assess the environmental risks of heavy metals (Cu, Pb, Zn, Cd, and Cr) and to understand discrepancies of risk assessment indices and urbanization effects regarding heavy metal contamination. Results showed that Cd, Zn, and Pb were the most enriched metals in urban sections assessed by I_geo and over 95% of the samples exceeded the Zn and Pb thresholds of the effect range low (ERL) of SQGs. According to RAC, Cu, Zn, Cd, and Cr had high risks of adversely affecting the water quality of the Grand Canal due to their remarkable portions of exchangeable fraction in surface sediment. However, Pb showed a relative low risk, and was largely bounded to Fe/Mn oxides in the urban surface sediments. Obviously, the three assessment indices were not consistent with each other in terms of predicting environmental risks attributed to heavy metals in the freshwater surface sediments of this study. It is recommended that risk assessment by SQGs should be revised according to availability and site specificity. However, the combination of the three indices gave us a comprehensive understanding of heavy metal risks in the urban surface sediments of the Grand Canal.