Toxicity assessment for petroleum-contaminated soil using terrestrial invertebrates and plant bioassays

The assessment of soil quality after a chemical or oil spill and/or remediation effort may be measured by evaluating the toxicity of soil organisms. To enhance our understanding of the soil quality resulting from laboratory and oil field spill remediation, we assessed toxicity levels by using earthworms and springtails testing and plant growth experiments. Total petroleum hydrocarbons (TPH)-contaminated soil samples were collected from an oilfield in Sfax, Tunisia. Two types of bioassays were performed. The first assessed the toxicity of spiked crude oil (API gravity 32) in Organization for Economic Co-operation and Development artificial soil. The second evaluated the habitat function through the avoidance responses of earthworms and springtails and the ability of Avena sativa to grow in TPH-contaminated soils diluted with farmland soil. The EC₅₀ of petroleum-contaminated soil for earthworms was 644 mg of TPH/kg of soil at 14 days, with 67 % of the earthworms dying after 14 days when the TPH content reached 1,000 mg/kg. The average germination rate, calculated 8 days after sowing, varied between 64 and 74 % in low contaminated soils and less than 50 % in highly contaminated soils.     

Polycyclic aromatic hydrocarbons (PAHs) in starfish body and bottom sediments in Mohang Harbor (Taean), South Korea

The concentrations of 27 polycyclic aromatic hydrocarbons (PAHs) were determined in bottom sediments and starfish from Mohang Harbor (MH) in Taean peninsula, South Korea. In December 2007, crude oil washed ashore from the M/V Hebei Spirit and was subsequently cleaned up within a few months of the incident. The ecological risk, bioaccumulation factor (BAF), and composition of the 27 PAHs were examined. The PAH concentrations in the bottom sediment ranged from 24 to 366 μg/kg dried weight, and the ecological risk was determined as minimal (mERL-Q?<?1). Total PAH concentrations in Asterina pectinifera (inside seawall) and Asterias amurensis (outside seawall) were 1,226 and 1,477 μg/kg dry weight (d.w.), respectively. The total BAFs (∑BAF) for A. amurensis was 3.8 times higher than that of A. pectinifera, and the PAH concentrations of 5–6 log K _OW were highest in the two starfish species. Further, PAH fingerprint analysis (nine alkyl-substituted PAHs fraction, low molecular weight (LMW)/high molecular weight (HMW), Phe/Ant, and Flu/Pyr), and principal component analysis (PCA) based on three crude oil samples from the M/V Hebei Spirit showed no remaining influence of crude oil.     

Polycyclic aromatic hydrocarbon concentrations,mutagenicity, and Microtox® acute toxicity testing of Peruvian crude oil and oil-contaminated water and sediment

The oil industry is a major source of contamination in Peru, and wastewater and sediments containing oil include harmful substances that may have acute and chronic effects. This study determined polycyclic aromatic hydrocarbon (PAH) concentrations by GC/MS, mutagenicity using TA98 and TA100 bacterial strains with and without metabolic activation in the Muta-ChromoPlate? test, and Microtox® 5-min EC₅₀ values of Peruvian crude oil, and water and sediment pore water from the vicinity of San José de Saramuro on the Marañón River and Villa Trompeteros on the Corrientes River in Loreto, Peru. The highest total PAH concentration in both areas was found in water (Saramuro?=?210.15 μg/ml, Trompeteros?=?204.66 μg/ml). Total PAH concentrations in water from San José de Saramuro ranged from 9.90 to 210.15 μg/ml (mean?=?66.48 μg/ml), while sediment pore water concentrations ranged from 2.19 to 70.41 μg/ml (mean?=?24.33 μg/ml). All water samples tested from Saramuro and Trompeteros sites, and one out of four sediment pore water samples from Trompeteros, were found to be mutagenic (P?<?0.001). One sediment pore water sample in Saramuro was determined to have a measurable toxicity (Microtox EC₅₀?=?335.1 mg/l), and in Trompeteros, the EC₅₀ in water and sediment pore water ranged from 25.67 to 133.86 mg/l. Peruvian crude oil was mutagenic using the TA98 strain with metabolic activation, and the EC₅₀ was 17.18 mg/l. The two areas sampled had very high PAH concentrations that were most likely associated with oil activities, but did not lead to acute toxic effects. However, since most of the samples were mutagenic, it is thought that there is a greater potential for chronic effects.     

Dissipation kinetics of tetraconazole in three types of soil and water under laboratory condition

Laboratory experiment was conducted to understand the persistence behavior of tetraconazole in three soils of West Bengal (alluvial, red lateritic, and coastal saline) and also in water maintained at three different pH (4.0, 7.0, and 9.2) conditions. Processed soil samples (100 g) were spiked at two treatment doses: 2.5 μg/g (T₁) and 5.0 μg/g (T₂). Double distilled buffered water (200 ml) was spiked at two treatment doses: 1.0 μg/ml (T₁) and 2.00 μg/ml (T₂). The tetraconazole dissipation followed first-order reaction kinetics and the residual half-life (T _1/2) values in soil were found to be in the range of 66.9–77.2 days for T₁ and 73.4–86.0 days for T₂. The persistence increased in the order red lateritic > new alluvial > coastal saline. Interestingly, the red lateritic soil exhibited the lowest pH (5.56) and organic carbon (0.52 %) content as compared to other two soils. However, the dissipation of tetraconazole in case of water was not pH dependant. The T _1/2 values in water were in the range of 94 to 125 days. The study indicated the persistent nature of tetraconazole in soil and water.     

Dissipation and residues of bispyribac-sodium in rice and environment

The dissipation and residues of bispyribac-sodium in rice cropping system were studied. Bispyribac-sodium residues were extracted by a simple analytical method based on QuEChERs and detected by LC-MS/MS. The limit of detection for bispyribac-sodium of this method was 0.375?×?10^?3 ng. The limit of quantification (LOQ) was 5.0 μg/kg for rice plant samples, 2.0 μg/kg for rice hull, 0.2 μg/kg for water, and 0.1 μg/kg for soil and husked rice samples. The average recoveries of bispyribac-sodium ranged from 74.7 to 108 %, with relative standard deviations less than 13 %. The half-lives of bispyribac-sodium in rice plant, water, and soil were in the range of 1.4–5.6 days. More than 90 % of bispyribac-sodium residue dissipated within 5 days. The final residues of bispyribac-sodium in rice were all below LOQ at harvest time.     

Toxicity of Hg, Cu and Zn on early developmental stages of the European clam (Ruditapes decussatus) with potential application in marine water quality assessment

The toxicity of mercury, zinc and copper on sperm viability, fertilisation and embryogenesis of Ruditapes decussatus was examined. Cu did not affect sperm viability at all the concentrations tested. Conversely, the Zn and Hg significantly (P?<?0.01) reduced sperm viability only at the highest concentration (respectively 512 and 256 μg/l). Cu caused a significant decrease (p?<?0.05) of less than 6% in the fertilisation rate at 128 μg/l and Zn of up to 13% at 64 μg/l. Hg significantly (p?<?0.01) inhibited fertilisation at concentrations as low as 32 μg/l. The median effective concentrations (EC50) reducing rates of embryogenesis by 50% were 21.1 μg Hg/l (0.1 μM), 46.3 μg Cu/l (0.72 μM) and 43.4 μg Zn/l. Therefore, Hg is up to seven times more toxic than Cu (on a molar basis). Ecotoxicity of mercury on larvae survival was also assessed in this work. Result showed a significant (p?<?0.05) reduction of survival after exposure to 4 and 12 μg/l of Hg. The fertilisation rate and embryogenesis were the most sensitive endpoints, although the latter is more advisable for routine assessment of seawater quality because of its greater sensibility.     

Biomagnifications of mercury and methylmercury in tuna and mackerel

Seawater may be contaminated by harmful substances, including toxic elements released by human activities. The present study evaluates the total mercury and methylmercury concentrations and their correlations to fish body size in longtail tuna and short-bodied mackerel from Chendring, Kuantan, at east coast and Kuala Perlis at west costs of Peninsular Malaysia during May to November 2007. Total mercury and methylmercury in muscle tissue of 69 samples of longtail tuna and short-bodied mackerel, ranged from 0.180 to 1.460 μg/g and 0.0.169–0.973 μg/g and 0.251–1.470 μg/g and 0.202–1.352, whereas the methylmercury to total mercury ratio ranged from 70% to 83%, respectively. Samples of both species from the east coast showed higher levels of mercury compared to those from west coast. In all of the locations, significant positive correlations were found between fish body weight and mercury content (R²?> 0.470). The estimated weekly intake of total mercury and methylmercury from the consumption 66.33 g/week of short-bodied mackerel and 18.34 g/week of longtail tuna (based on local dietry survey) was found to be lower than the maximum limit of 5 and 1.5 μg/kg bodyweight established by FAO/WHO and codex, respectively.     

Alkylphenols and polycyclic aromatic hydrocarbons in eastern Mediterranean Spanish coastal marine bivalves

This paper reports the first results on alkylphenol pollution in edible bivalves from the Spanish coast. Two sampling campaigns (July 2006 and July 2007) were carried out to determine the concentration of nonylphenol (NP), octylphenol (OP), and eight polycyclic aromatic hydrocarbons (PAHs) in wild mussels (Mytilus galloprovincialys) and clams (Donax trunculus) at 14 sampling sites along the eastern Mediterranean Spanish coast. The results show that NP is the predominant alkylphenol, being the port of Valencia the most polluted area (up to 147 ??g/kg wet weight in clams). Moving away from the ports the concentration of NP in bivalves decreased. OP concentration was below its detection limit in most of the studied areas and its maximum concentration (6 ??g/kg w/w) was measured in clams from the port of Sagunto. The presence of low levels of PAHs was observed in most of the studied areas. The total PAHs concentration (i.e., sum of the eight measured PAHs) achieved a maximum value of 10.09 ??g/kg w/w in the north coast of Valencia city. The distribution pattern of the individual PAHs showed that both pollution sources petrogenic and pyrolytic were present in the sampled areas. Fluoranthene was the most abundant PAH in mussels while benzo(b)fluoranthene in clams. The maximum concentration of 10 ??g/kg w/w for benzo(a)pyrene established by the European Commission was never reached, indeed sampled bivalves showed concentrations 10 times lower than this reference value. Thus, they can be considered safe for human consumption. Despite the low contamination levels, the results show an overall pollution of bivalves by alkylphenol and PAHs as well as an increment in the number of polluted areas from 2006 to 2007. Thus, periodical sampling campaigns should be carried out to monitor the long-term tendency of these toxic and persistent pollutants.     

Simultaneous derivatization and extraction of nitrophenols in soil and rain samples using modified hollow-fiber liquid-phase microextraction followed by gas chromatography–mass spectrometry

A simple and sensitive method based on a modified hollow-fiber liquid-phase microextraction followed by gas chromatography–mass spectrometry has been successfully developed for the extraction and simultaneous derivatization of some nitrophenols (NPs) in soil and rain samples. Microwave-assisted solvent extraction was used for the extraction of NPs from the soil, while the rain sample was directly applied to the previously mentioned method. Briefly, in this method, the analytes were extracted from aqueous samples into a thin layer of organic solvent (dodecane?+?10 % tri-n-octylphosphine oxide) sustained in the pores of a porous hollow fiber. Then, they were back-extracted using a small volume of organic acceptor solution (25 μl; 10 mg/L N-methyl-N-(trimethylsilyl)trifluoroacetamide, as derivatization reagent, in acetonitrile) that was located inside the lumen of the hollow fiber. Under the optimized extraction conditions, enrichment factors of 255 to 280 and limits of detection of 0.1 to 0.2 μg/L (S/N?=?3) with dynamic linear ranges of 1–100 μg/L were obtained for the analytes. The accuracy of the approach was tested by the relative recovery experiments on spiked samples, with results ranging from 93 to 113 %. The method was shown to be rapid, cost-effective, and potentially interesting for screening purposes.     

Physicochemical properties and mineral contents of seven different date fruit (Phoenix dactylifera L.) varieties growing from Saudi Arabia

The date (Phoenix dactylifera L.) fruits (Soukari, Soulag, Barhi, Khulas, Rozaiz, Soughi and Monaif) were evaluated with respect to some physical and chemical properties. While crude protein contents of fruits change between 1.51 % (Soulag) to 2.41 % (Soughi), crude fibre contents ranged between 1.91 % (Soukari) to 3.90 % (Barhi). Vitamin C contents of date samples changed between 971.82 mg/kg (Soughi) to 1,453.15 mg/kg (Barhi). Antioxidant activity of date fruits ranged from 80.07 IC₅₀ (Soukari) to 81.21 IC₅₀ (Soulag). The highest phenolic content was found in Khulas with a mean value of 198 mg GAE/100 g. Energy values of date fruits ranged from 3,725 kcal/kg (Soulag) to 3,870 kcal/kg (Soukari). Sucrose contents of date fruits changed between 1.02 % (Soulag) to 55.71 % (Soukari). Mineral contents of several date fruits were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). Date samples contain potassium at a range between 7,468 mg/kg (Khulas) to 9,619 mg/kg (Soulag). Phosphorus contents of fruits were found between 1,848 mg/kg (Soulag) to 3,066 mg/kg (Rozaiz) and followed by magnesium and calcium. The highest Zn (9.33 mg/kg), Cu (4.27 mg/kg) and Mn (3.26 mg/kg) were found in Rozaiz, Soukari and Barhi samples, respectively.     

Mercury accumulation in caged Corbicula: rate of uptake and seasonal variation

The uptake and seasonal fluctuations of total mercury were followed in caged and uncaged Asiatic clams, Corbicula fluminea, over a 1-year period in South River, Virginia. Mercury was rapidly accumulated in clams transplanted from a nominally uncontaminated site into cages on the contaminated South River, reaching 0.99 μg g^???1 dry mass within the first month. Resident clams moved to cages had higher mercury contents after the first month (2.04 μg g^???1 dry mass) and at all subsequent times in the study. Large monthly fluctuations in mercury were noted for both resident caged and transplant caged clams with a notable peak occurring in early spring (4.31 μg g^???1 dry mass in resident caged clams). Tissue mass of caged clams steadily increased through the winter and early spring. Adjustment of mercury concentrations for tissue mass changes indicated that the changes in mercury contents were primarily due to uptake/release rather than changes in tissue mass (concentration/dilution). The present study demonstrates the utility of using caged Corbicula as mercury biomonitors and illustrates the importance of accounting for large, short-term changes of mercury content in Corbicula when designing long-term biomonitoring studies.     

Voltammetric trace determination of mercury using plant refuse modified carbon paste electrodes

Citrus limon peel (kitchen waste) and Leucaena leucocephala seeds (agricultural waste) were used as a modifier for fabrication of modified carbon paste electrode for determination of mercury in aqueous sample using differential pulse anodic stripping voltammetry. Mercury was adsorbed on electrode surface at open circuit and anodic stripping voltammetric scan was run from ?0.5 to 0.5 V. Various electrochemical parameters including amount of modifier, supporting electrolyte, accumulating solvent, pH of the accumulating solvent, and accumulation time were investigated. The effect of presence of other metal ions and surfactants was also studied. In comparison C. limon peel proved to be a better modifier than L. leucocephala seed biomass. This was justified by electrode characterization using cyclic voltammetry that indicated decrease in resistance of electrode when C. limon peel was used as modifier and increase when modifier was L. leucocephala seeds. Maximum current response was obtained using 5 % C. limon peel biomass, hydrochloric acid as supporting electrolyte, acetate buffer of pH 6 as an accumulating solvent, 10-min accumulation time, and scan rate of 50 mV/s. Linear calibration curves were obtained in the concentration range 100 to 1,000 μg L^?1 of mercury for accumulation time of 10 min with limit of detection of 57.75 μg L^?1 and limit of quantification of 192.48 μg L^?1. This technique does not use mercury as electrode material and, therefore, has a positive environmental benefit.     

Rapid spectrophotometric determination of trace amounts of palladium in water samples after dispersive liquid–liquid microextraction

A simple, rapid, and efficient dispersive liquid–liquid microextraction method, followed by UV–Vis spectrophotometry was developed for the preconcentration and determination of Pd ions in water samples. Pd ions react with α-furildioxime (chelating agent) to form a hydrophobic complex. Various parameters were altered to study and optimize their effects on the extraction efficiency, such as pH, ligand concentration, the type and volume of extraction and dispersive solvents, extraction time, and salt concentration. Under optimized conditions, the method exhibited an enrichment factor (C _org/C _aq) of 25 and recovery more than 98 % within a very short extraction time. The linearity of the method ranged from 10 to 200 μg?L^?1. The limit of detection was 1.1 μg?L^?1. The relative standard deviation for the concentration of 100 μg?L^?1 of Pd was 2.3 % (n?=?10). Finally, the developed method was successfully applied to the extraction and determination of Pd in tap, river, mineral, and sea water samples.     

Assessment of indoor and outdoor particulate air pollution at an urban background site in Iran

The relationship between indoor and outdoor particulate air pollution was investigated at an urban background site on the Payambar Azam Campus of Mazandaran University of Medical Sciences in Sari, Northern Iran. The concentration of particulate matter sized with a diameter less than 1 μm (PM_1.0), 2.5 μm (PM_2.5), and 10 μm (PM₁₀) was evaluated at 5 outdoor and 12 indoor locations. Indoor sites included classrooms, corridors, and office sites in four university buildings. Outdoor PM concentrations were characterized at five locations around the university campus. Indoor and outdoor PM measurements (1-min resolution) were conducted in parallel during weekday mornings and afternoons. No difference found between indoor PM₁₀ (50.1 ± 32.1 μg/m³) and outdoor PM₁₀ concentrations (46.5 ± 26.0 μg/m³), indoor PM_2.5 (22.6 ± 17.4 μg/m³) and outdoor PM_2.5 concentration (22.2 ± 15.4 μg/m³), or indoor PM_1.0 (14.5 ± 13.4 μg/m³) and outdoor mean PM_1.0 concentrations (14.2 ± 12.3 μg/m³). Despite these similar concentrations, no correlations were found between outdoor and indoor PM levels. The present findings are not only of importance for the potential health effects of particulate air pollution on people who spend their daytime over a period of several hours in closed and confined spaces located at a university campus but also can inform regulatory about the improvement of indoor air quality, especially in developing countries.     

Emission characteristics of VOCs from three fixed-roof p-xylene liquid storage tanks

This study evaluates emission characteristics of volatile organic compounds (VOCs) caused by standing loss (L _S) and working loss (L _W) of three vertical fixed-roof p-xylene (p-X) liquid tanks during 1-year storage and filling operation. The annual net throughput of the tanks reached 70,446 t, resulting in 9,425 kg of p-X vapor emission including 5,046 kg of L _S (53.54 %) and 4,379 kg of L _W (46.46 %). The estimated L _W of AP-42 displayed better agreement with the measured values of a VOC detector than the estimated L _S of AP-42. The L _S was best correlated with the liquid height of the tanks, while the L _W was best correlated with the net throughput of the tanks. As a result, decreasing vapor space volume of the tanks and avoiding high net throughput of the tanks in a high ambient temperature period were considered as effective means to lessen VOC emission from the fixed-roof organic liquid storage tank.     

Health risk assessment of mercury and arsenic associated with consumption of fish from the Persian Gulf

Concentrations of mercury and arsenic in fish from the Persian Gulf were determined by graphite furnace atomic absorption spectrometry. Concentrations of the metals in muscle samples were 0.049–0.402 μg g^?1 for mercury and 0.168–0.479 μg g^?1 for arsenic, with means of 0.133 and 0.312 μg g^?1, respectively. The maximum daily consumption rate (grams per day) and meal consumption limit (meals per month) was calculated to estimate health risks associated with fish consumption. According to the results, the maximum allowable consumption rate varies between 8–56 and 15–96 g/day base on mercury and arsenic content, respectively. The results of this study indicate that the concentration of mercury and arsenic is well below the maximum permissible levels for mercury (0.5 μg g^?1) and arsenic (6 μg g^?1) according to international standards.     

Blood levels of cadmium and lead in residents near abandoned metal mine areas in Korea

We analyzed national data on blood lead levels (BLL) and blood cadmium levels (BCL) in residents living near 38 abandoned metal mining areas (n?=?5,682, 18–96 years old) in Korea that were collected by the first Health Effect Surveillance for Residents in Abandoned Metal mines (HESRAM) from 2008 to 2011. The geometric mean BCL and BLL were 1.60 μg/L (95 % CI?=?1.57–1.62 μg/L) and 2.87 μg/dL (95 % CI?=?2.84–2.90 μg/dL), respectively, notably higher than levels in the general population in Korea and other countries. We found significantly higher BLL and BCL levels in people living within 2 km of an abandoned metal mine (n?=?3,165, BCL?=?1.87 μg/L, BLL?=?2.91 μg/dL) compared to people living more than 2 km away (n?=?2,517, BCL?=?1.31 μg/L, BLL?=?2.82 μg/dL; P?<?0.0001) and to the general population values reported in the literature.     

Analysis of heavy metals in marine fish from Mumbai Docks

Seafood containing heavy metals as a result of environmental contamination causes toxicity in human beings. To evaluate such kind of contamination, our study targeted the analysis of metals such as lead, copper, cadmium, mercury, and arsenic in muscle tissue of the fish. The fish commonly consumed such as Brama brama (Pomfret), Rachycentron canadus (Surmai/King Fish), Rastrelliger kanagurta (Mackerel), Eleutheronema tetradactylum (Ravas/Indian salmon), and Metapenaeus monoceros (Brown Prawn) were collected from four different docks in the city. The heavy metals in tissue samples of fish were estimated using voltammeter and cold vapor atomic absorption spectrophotometer. Heavy metal concentration in the tissues varied significantly depending upon the locations from where the fish were collected. Although the concentration of arsenic, copper, cadmium, and lead were in normal range, the concentration of mercury was found to exceed the daily permissible levels (1 μg/g) as a food source for human consumption. We have analyzed heavy metals from different locations in Mumbai—Versova dock, Sassoon dock, Navi Mumbai dock, and Mazgaon dock.     

Cloud point extraction–atomic absorption spectrometry for pre-concentration and determination of cadmium in cigarette samples

A new complexing agent, 2-((2-((1H-benzo[d]imidazole-2yl)methoxy)phenoxy)methyl)-1H-benzo[d]imidazole (BIMPI), was used in cloud point extraction and applied for selective pre-concentration of trace amounts of cadmium in cigarette samples. Cadmium was complexed with BIMPI in a buffer solution (pH?=?10) using Triton X-114 as surfactant and quantitatively extracted into a small volume of the surfactant-rich phase after centrifugation. Under optimized conditions (pH?=?10.0, 0.8?×?10^?4?mol?L^?1 BIMPI and 0.08 % (w/v) Triton X-114), calibration graph was linear in the range of 34.0–1,670.0 μg?L^?1. The proposed method was applied to the determination of Cd in various cigarette (tobacco) samples which gave satisfactory results.     

Re-construction of the shut-down PM10 monitoring stations for the reliable assessment of PM10 in Berlin using fuzzy modelling and data transformation

A dense monitoring network is vital for the reliable assessment of PM10 in different parts of an urban area. In this study, a new idea is employed for the re-construction of the 20 shut-down PM10 monitoring stations of Berlin. It endeavours to find the non-linear relationship between the hourly PM10 concentration of both the still operating and the shut-down PM10 monitoring stations by using a fuzzy modelling technique, called modified active learning method (MALM). In addition, the simulations were performed by using not only raw PM10 databases but also log-transformed PM10 databases for skewness reduction. According to the results of hourly PM10 simulation (root mean square error about 13.0 μg/m³, correlation coefficient 0.88), the shut-down stations have been appropriately simulated and the idea of dense monitoring network development by the re-construction of the shut-down stations was realised. The results of simulations using raw and log-transformed databases showed that data transformation has no significant effect on the performance of MALM in the simulation of shut-down PM10 stations. By the combination of the 11 still operating stations and the 20 re-constructed stations, a dense monitoring network was generated for Berlin and was utilised for the calculation of the reliable monthly and mean annual PM10 concentration for five different PM10 zones in Berlin (the suburban-background, urban-background, urban-traffic, rural-background and suburban-traffic areas). The results showed that the mean annual concentration of PM10 at the five zones increased by about 13.0% in 2014 (26.3 μg/m³) in comparison with 2013 (23.3 μg/m³). Furthermore, the mean annual concentration of PM10 in the traffic lanes of the suburban (2013 25.0 μg/m³, 2014 26.9 μg/m³) and urban (2013 27.7 μg/m³, 2014 31.3 μg/m³) areas is about 14 and 20% higher than the PM10 concentration of suburban-background (2013 21.3 μg/m³, 2014 24.5 μg/m³) and urban-background (2013 23.0 μg/m³, 2014 26.1 μg/m³) areas, respectively.