Polycyclic Aromatic Hydrocarbons in Sediments: An Overview of Risk-Related Issues

This series of articles address site-specific issues associated with evaluating exposure and toxicity of polycyclic aromatic hydrocarbons (PAHs) in sediments. These include factors that influence the opportunity to come into contact with PAHs in sediments (bioaccessibility) and those that affect the potential for transfer from sediment to ecological and human receptors (bioavailability). Although organic carbon is viewed as an important matrix for sorbing PAHs, studies have shown that there are various forms of carbon, some of which are highly sorptive. These latter forms vary on a site-specific basis and including this form of carbon in the assessment can reduce the uncertainty associated with estimating exposure. Other site-specific factors associated with water clarity, depth, and light penetration can result in enhanced toxicity of PAHs as a result of photoactivation. Chemical analyses of sediments increasingly include the alkylated PAH compounds. Although analyses of this suite of PAH compounds is being conducted to support ecological assessments and forensic analyses, there is little guidance on how to interpret the alkylated PAHs with respect to human health risks. An approach for accomplishing this is suggested.     

Source apportionment and risk assessment of PAHs in Brisbane River sediment,Australia

Sediment samples collected over a 3-year period from Brisbane River, Australia, were analysed for fifteen (15) polycyclic aromatic hydrocarbons (PAHs). The total PAH concentrations varied from 148 to 3079 ng/g with a mean concentration of 849 ± 646 ng/g. The study revealed that PAH input into the river was primarily dominated by pyrogenic sources as evidenced by the predominance of the high molecular weight (HMW) PAHs. Temporal variations of PAHs can be linked to the level of urbanization, with continuous input of combustion related PAHs in the commercial area of the river. Inherent deficiencies in using a single source identification/apportionment approach were overcome by using diagnostic ratios, principal component analysis/absolute principal component scores (PCA/APCS) and positive matrix factorization (PMF). Both, PCA/APCS and PMF resolved four (4) identical factors or sources of PAHs, namely: gasoline emissions, diesel emissions, biomass burning and natural gas combustion. Diagnostic ratios, PCA/APCS and PMF analysis indicated that vehicular emissions were the principal sources especially within the lower section of the river while biomass burning had moderate contribution. The distribution, temporal trend and source apportionment suggest the containment of industrial-derived sources of PAHs in the river. From an ecological point of view, the risk posed by PAHs in the Brisbane River sediment appears to be low. Nevertheless, when the investigated sites were ranked using multi-criteria decision making methods(MCDM) the commercial stratum was the most contaminated. Assessment of potential risks posed by incidental dermal exposure to PAHs revealed some degree of cancer risk, especially to children.     

Sources of PAHs to Sediments of the Elizabeth River,VA

Sediments collected from the Elizabeth River, VA, a highly contaminated subestu-ary of the James River, were analyzed for polycyclic aromatic hydrocarbons (PAHs). Select isomer ratios (BbF/BkF, BaA/chrysene, and IP/BghiP) and molecular weight fractions (ΣPAH_202/202-276 and ΣPAH_252/202-276) were identified as source indicators for two former wood-treatment facilities (Atlantic Wood and Eppinger & Russell) located on the southern branch of the Elizabeth River. These facilities are suspected as probable contributors to the high PAH contamination in sediments. Plots of the wood-treatment source indicators, along with those for coal, wood, and automotives, revealed a likely contribution from only one of the former wood-treatment facilities, in addition to the possible contribution of coal/coal gasification to PAH contamination in sediments of the main stem and southern branch of the Elizabeth River. By examining PAH isomer ratios from known or suspected sources, it is possible to distinguish multiple sources of PAHs to an ecosystem.     

Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Sediments of Lake Manzala,Egypt

This investigation represents the first extensive study of the spatial distribution, sources, and potential effects of polycyclic aromatic hydrocarbons (PAHs) in sediments from Lake Manzala, the largest of Egypt's Mediterranean coastal lakes. The concentrations of PAHs (Σ39 components) ranged from 246 to 9910 ng g^?1 dry wt., the highest values corresponding to urban hotspots with high anthropogenic input coming from wastewater discharges and combustion activities and decreasing offshore. The levels of PAHs were significantly lower compared to values reported in several coastal/estuarine areas (e.g., in Spain, Italy, USA, and Egypt) receiving substantial anthropogenic inputs from urban and industrial activities. Source ratios indicated that the PAHs were mainly from petrogenic sources in near-shore urban hotspots, with higher contributions of pyrolytic sources in coastal and offshore areas which are little influenced by human activities. Sediment quality guidelines (SQGs) showed that except at one station heavily impacted by sewage discharge, the total and individual PAH concentrations were below effect range low (ERL) concentrations that are not likely to adversely affect benthic biota.     

小冶炼地区PAHs污染及其风险评价

采样分析了中国东部沿海某镇小冶炼地区多介质环境中 PAHs的浓度水平 ,发现小冶炼集中生产区内大气中 17种PAHs总浓度 (Σ PAHs)高达 4 170 ng/ m3,是区外大气中 Σ PAHs平均值的 6倍 ;该区内河及边境河流下游河水中 Σ PAHs平均为 8.17μg/ L ,远大于边境河流上游河水中的Σ PAHs平均值 (2 .17μg/ L ) ;表层水稻土中Σ PAHs平均为 15 2 mg/ kg,并随着土壤深度增加逐渐减少 ;水稻根、茎叶、籽实中Σ PAHs平均分别为 5 2 9μg/ kg、5 39μg/ kg、10 5μg/ kg。类比调查表明 ,小冶炼地区各环境介质中的 PAHs浓度均不同程度地高于文献报道值。估算了当地居民及冶炼工人经呼吸进入体内的 8种致癌 PAHs的量 ,分别达 5 30 ng/ d和 1138ng/ d。调查了小冶炼地区及其周围地区近 3a死亡人群的死因 ,发现该区死亡人群中病死比例和死于癌症比例平均分别达 32 .2 %和 2 5 .6 % ,均高于周围地区的相应值 (2 3.3%和 16 .0 % )     

Risk assessment of polycyclic aromatic hydrocarbons (PAHs) in sediments from a mixed-use reservoir

Although reservoirs in China are of great significance, very few studies on risk assessment have been reported for reservoirs. This study investigated distribution characteristics, cancer and ecological risks, and source diagnosis of 16 priority polycyclic aromatic hydrocarbons (PAHs) in sediments from Shitou Koumen Reservoir in Jilin Province, China. A total of 12 sediment samples were collected from the reservoir in August (wet season) 2014. Total PAH concentrations in sediment samples ranged from 1294.51 ng/g to 2755.35 ng/g with a mean concentration of 1757.54 ng/g. For individual PAHs, average concentration of Nap was the highest, 800.56 ng/g, while Acy, Fla, BkF, and DahA were undetected in sediment samples. Light PAHs (2–3 rings) accounting for 74.21% was a dominant PAH compositional pattern. Pearson correlation analysis was carried out; results showed that total PAHs was strongly correlated with the highly enriched sedimentary PAHs, and pH was a major factor in controlling PAH distribution. Lifetime cancer risk was employed to assess cancer risk; results indicated that the fish-culturing area was exposed to cancer risk. The molecular diagnostic ratios of isomeric PAHs were applied to identify possible PAH sources; primary PAH sources were identified as oil-related activities, burning agricultural wastes, vehicular emissions, and industrial discharges.     

Ants as Bioindicators of Natural Succession in Savanna and Riparian Vegetation Impacted by Dredging in the Jequitinhonha River Basin,Brazil

We investigated the response of ant species to landscape and geomorphologic parameters of a long‐term (7–11 years) restoration project in the Jequitinhonha River (Northern State of Minas Gerais, Brazil) margins, previously dredged by a diamond mining company. Geomorphological changes from the dredging were severe and the area is unlikely to be adequately restored, mainly due to the negative effects of flooding. Our hypothesis is that ant species assemblages bioindicate successional stages and soil characteristics. We studied the association of effects from the river's flooding zone, the native vegetation, and sedimentary grain size with that of ant species diversity, abundance, and composition. An ant sampling program was conducted in April 2005, using three methods: baits, pitfall traps, and direct collection. Grain size was measured by sieving. In total, 10,784 ants were sampled, belonging to 7 subfamilies, 24 genera and 45 morphospecies. Ant species richness was greater in the undisturbed savanna area than in the restored habitats, and equivalently greater in the ecotone and intermediate zone habitats than on the river bank, the poorest habitat. Atta sexdens rubropilosa indicated a condition related to small forest remnants having well‐structured soil. On the other hand, ants with a body length of under 0.5 cm (Dorymyrmex pyramicus and Pheidole fallax) predominated in sandy areas, where the majority of the granules were the finest. The lack of organic matter and soil structure for constructing suitable nests may prevent large ants from colonizing such areas, and thus inhibit the advance of natural succession.     

Distribution,Sources Identification,and Ecological Risk of PAHs and PCBs in Coastal Surface Sediments from the Northern Persian Gulf

Hormozgan Province plays a vital role in fishery, petroleum, and industrial activities in southern Iran. However, no comprehensive studies on organic pollution have been performed. PCBs and PAHs were analyzed in surface sediments from areas receiving industrial (nine sites), river (one site), and urban (two sites) effluents. The sediment samples were collected in March and September 2010 (in dry and wet seasons) at the highest tidal time. The overall pollution level of PCBs ranged from 2.5 ± 0.8 to 462.0 ± 206.7 ng/g dry weight. CB153 congener dominated in most of the sediment samples. Congener profiles of PCBs showed close similarity with formulations of commercial products such as Aroclor 1260 and 1254 g. A wide range of 55.3 to 1231.6 ng/g dry weight was detected for ∑PAHs. Results of PCA and PCA-MLR tests confirmed both petrogenic and pyrogenic origins for PAH pollution. The higher means of ∑PAHs and ∑PCBs in industrial and urban wastewaters were found near the shore, evidencing the role of these wastewaters in the PAH and PCB contamination in Hormozgan sediment. The concentrations of PAHs and PCBs in detected hotspots exceed the U.S. NOAA sediment quality guidelines.     

Evaluation of PAHs concentration and cancer risk assessment on human health in a roadside soil: A case study

Abstract

An explanatory study was carried out to divulge the sources, contamination level of different classes of Polycyclic Aromatic Hydrocarbons (PAHs) distribution and the impact of vehicular traffic on the roadside soil by assessing incremental lifetime cancer risk at each site to understand the potential health risk of nearby residents along the National Highway-2 Delhi–Kolkata India. Comparison of the cancer risk assessment was performed using Monte Carlo simulation for the entire study area. The results revealed 90% cancer risk value of 6.40?×?10^?5 and 6.5?×?10^?5 for children and adults, respectively, whereas, without simulation the Total Cancer Risk (TCR) for adults was 6.925?×?10^?5 and 6.220?×?10^?5 for children, observed maximum at the location (S5). The dilemma of risk assessment indicating profoundly contaminated soil. Comparison of PAHs concentration with the background values of PAHs ranged from 1.478 to 27.493?mg kg^?1. The (IP/BgP) ratio specified that the PAHs content of the highway roadside sample is preponderate by diesel vehicle emission, biomass combustion and coal combustion. The study clearly revealed and advocated the influence of organic and inorganic pollution, which aggravates and causes health issues to the nearby inhabitants. This study could also be advantageous to similar consequences seen elsewhere in the world.     

Trace Metal Fractionation by the Sequential Extraction Method in Sediments from the Lis River (Portugal)

The extractable contents of Zn, Pb, Cu, Cr, Mn, Ni, Fe and Al were evaluated in sediments from the Lis River (Portugal) using the three-step sequential extraction procedure described by Community Bureau of Reference (BCR, now the Standards, Measurement and Testing Programme) of the European Union. The distribution of trace metals among the exchangeable, water and acid soluble, reducible, oxidizable and residual fractions was determined. The highest metal concentrations were observed in samples collected at the most polluted river sites (animal husbandry, domestic, industrial and agricultural wastes). Pb, Cu, Cr, Ni, Fe and Al were found mainly associated with the residual and organic fractions. High concentrations of Zn and Mn were found in the exchangeable/acid soluble fraction.     

Distribution of nutrients,trace elements,PAHs and radionuclides in sediment cores from Lake Varese (N. Italy)

Sediment cores were collected at 5 stations in Lake Varese. They were analyzed for organic matter, N, P, organic C, Cd, Cr, Cu, Hg, Pb, Zn and PAHs. A sedimentological approach has been applied to estimate the ecological risk from identified pollutants.As in other eutrophic lakes in Northern Italy, this lake is also at considerable risk from heavy metal pollution. Cr, Cu and Cd showed the highest enrichment factors for the last 5 years, 23.4, 8.0 and 7.6 respectively. Other metals had enrichment factors ranging from 1 to 3. Fluoranthene was chosen as a representative PAH, derived from combustion products; its average value in surficial sediments ranged from 100 to 220 ng l^-1 dw. This compound can be a hazard to human health and aquatic life. An evaluation of radionuclide distributions after the recent Chernobyl accident in the USSR (¹³⁴Cs, ¹³⁷C s, ¹³¹I, ¹⁰⁶Ru) provided useful tracers to follow the cycling of pollutants bound to particulate matter in the aquatic ecosystem.     

A Perspective on the Toxicity of Petrogenic PAHs to Developing Fish Embryos Related to Environmental Chemistry

Numerous studies demonstrate polynuclear aromatic hydrocarbons (PAHs) dissolved from weathered crude oil adversely affect fish embryos at 0.5 to 23 μg/l. This conclusion has been challenged by studies that claim (1) much lower toxicity of weathered aqueous PAHs; (2) direct contact with dispersed oil droplets plays a significant role or is required for toxicity; (3) that uncontrolled factors (oxygen, ammonia, and sulfides) contribute substantively to toxicity; (4) polar compounds produced by microbial metabolism are the major cause of observed toxicity; and (5) that based on equilibrium models and toxic potential, water contaminated with weathered oil cannot be more toxic per unit mass than effluent contaminated with fresh oil. In contrast, several studies demonstrate high toxicity of weathered oil; shifts in PAH composition were consistent with dissolution (not particle ablation), embryos accumulated dissolved PAHs at low concentrations and were damaged, and assumed confounding factors were inconsequential. Consistent with previous empirical observations of mortality and weathering, temporal shifts in PAH composition (oil weathering) indicate that PAHs dissolved in water should (and do) become more toxic per unit mass with weathering because high molecular weight PAHs are more persistent and toxic than the more abundant low molecular weight PAHs in whole oil.     

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.     

Probabilistic Risk Assessment of Polycyclic Aromatic Hydrocarbons (PAHs) in Produced Water

The produced water extracted during oil and gas production includes formation water, injected water, small volumes of condensed water, and any chemical added during the oil/water separation process. Produced water contains both organic and inorganic constituents, and several studies have been conducted in the past to assess their risk. The toxicity and persistence of polycyclic aromatic hydrocarbons (PAHs) in produced water is of particular environmental concern, but there are very few studies on human health risk assessment from PAHs of produced water. This article summarizes the results of a conservative human health risk assessment approach for PAHs in produced water discharges to the marine environment. Due to the absence of available toxicity data for PAHs, the cancer slope factors were determined by using the relative potency factors (RPF) and Toxicity Equivalency Factors (TEF). Using the concentration distribution factors, the maximum cancer risks to humans were predicted in the range of 4.07 × 10^?7 to 2.95 × 10^?6. The 95th-percentile values show that the risks are well within the acceptable limits.     

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.     

Distribution Characteristics and Risk Assessments of PAHs in Fish from Lake Taihu,China

The concentrations of PAHs in four species of fish (Common carp, Crucian carp, Bighead carp, and Topmouth culter) from Lake Taihu were tested, and the human health risks of PAHs by fish consumption were evaluated. Results showed that concentrations of PAHs in fish from Lake Taihu were 52.5–247.6 ng/g wet weight (ww), and the BaP equivalent concentrations of total PAHs (B[a]P_eq) were 0.2–0.6 ng/g ww, which were less than the screening value of 2.6 ng/g wet for human consumption. The concentration sequences of PAHs in fish from Lake Taihu from high to low were Bighead carp > Crucian carp > Common carp > Topmouth culter. The human health risk level of PAHs by fish consumption was 5.8 ± 2.5 × 10^?6, which was less than the maximum acceptable risk level of 1 × 10^?5 for human health set by the U.S. Environmental Protection Agency. The tissue residue guideline (TRG) of PAHs for protecting aquatic wildlife was 1.3 mg/kg diet ww, which was higher than the concentrations of PAHs in fish from Lake Taihu. The results indicated that fish consumption from Lake Taihu would not cause health risk or harmful effects on wildlife that consume aquatic biota.     

Seasonal variations of metal pollution and distribution,sources, and ecological risk of polycyclic aromatic hydrocarbons (PAHs) in sediment of the Al Hawizah wetland,Iran

The pollution of surface sediments of Al Hawizah wetland by metals and polycyclic aromatic hydrocarbons (PAHs) has been fully investigated. For determination of PAHs and metals concentration in sediments, eight sampling stations were selected in the study area. The results showed that the concentration of Mn is the highest, while the content of Cr is the lowest in both the seasons. The concentration of Cr and V is lower than mean crust content, while Cu concentration is more than mean crust content. The results obtained from Muller's geochemical index are indicative of range from uncontaminated to moderately contaminated. Based on potential ecological risk (RI), the Al Hawizah wetland had low ecological risk. The total PAHs concentrations ranged from 1071 to 15540 ng/g dry weight, with a mean of 9417.50 ng/g in the summer, while total amounts of PAHs in the winter ranged from 1542 to 17283 with a mean 10321.25 ng/g dry weight. The area of study was affected by pyrogenic and petrogenic sources (51.74 and 48.26%, respectively), in the winter. The concentrations of polycyclic aromatic hydrocarbons (PAHs) compounds were lower than effects range median (ERM) standard while were higher than effects range low (ERL) standard, except station 1, in both seasons.     

Experimental Study of Mobility and Kinetic Characterization of Trace Elements in Contaminated Sediments from a River Basin in Northern Peru

In the Jequetepeque basin (Peru), gold extraction activity has been performed in the last decades, leading to a release of metals and metalloids into the environment. Sediment samples were taken in the vicinity of two mines and analyzed. Extraction of metals and metalloids from sediments was carried out using single extraction procedures, acidic (HNO₃), and complexation (EDTA) leaching, in order to determine the mobility of trace elements. Results indicated that acidic extraction at low pH values increased the leachability of trace elements. EDTA showed a higher bioavailability of metals in sediments than acidic extraction under similar pH conditions because of its greater leaching capacity. This is an important issue in view of risk assessment analysis. The highest extractability was observed for Cd in all sediments with up to 90% of extraction after 1 h. The mobility index analysis indicated that faster kinetic leachability of some trace elements leads to a higher mobility in sediments, especially those near the active gold extraction mine. The ecological risk assessment suggested that the four river sediments were at high and very high risk levels, indicating that sediment contamination is an issue of environmental concern in the Jequetepeque basin of northern Peru.     

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.