Toxic Equivalency Quotient Research Articles

Detoxification modification of coal-tar pitch by ultraviolet & microwave radiation-enhanced chemical reaction and toxicity evaluation by chemical index and cytotoxicity assay in vitro

Although coal tar pitch (CTP) has a large yield in China, its large-scale and effective utilization is significantly hindered because of existing and possibly releasing polycyclic aromatic hydrocarbons (PAHs). Therefore, it is an imminent problem how to prepare an environmentally friendly CTP by detoxification modification. In the investigation, a typical CTP was subjected to structural characterization via solid-state 13C NMR and gas chromatograph/mass spectrometer, which confirmed the existence of dominant PAHs such as fluoranthene, pyrene, as well as benzo[a]pyrene, and few heterocyclic compounds. Subsequently, the CTP was modified using 10-undecenal via alkylation reaction enhanced by ultraviolet & microwave radiation. Compared with the original CTP, the total content of 16 toxic PAHs in the modified CTP decreased with a reduction efficiency of above 90%. According to different environmental standards, toxic equivalent quotient of CTP after modification was reduced by above 90%. In order to veritably and fully evaluate the toxicity of CTP, a living vascular smooth muscle cell (A-10 cell) in vitro was used in the cell counting kit-8 assay. The viability of A-10 cell was always higher when exposed to modified CTP than the original CTP. These results powerfully indicated that the enhanced modification was actually effective and efficient for reducing the toxicity of CTP.

Validation of proximity-based estimates of residential exposure to emissions of dioxins and dioxin-like compounds in the U.S.

Background: Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) are persistent organic pollutants emitted from industrial sources. The relationship between proximity to emissions from these sources and personal exposure is poorly understood.Methods: We linked geocoded residential addresses and serum measurements of PCDDs, PCDFs, PCBs, and their derived TEQ (toxic equivalency quotient) for 5,725 participants in the 1999-2004 U.S. National Health and Nutritional Examination Survey (NHANES) to a U.S. Environmental Protection Agency database of 4,478 historical emission sources of dioxins and dioxin-like compounds (e.g., coal-fired power plants, solid waste incinerators). We calculated continuous and categorical (3, 5, 10km) exposure metrics reflecting distance to the nearest facility and estimated intensity of exposure with a distance- and toxicity-weighted average emissions index (AEI [ng TEQ/km2]). We used linear regression models to evaluate associations between proximity metrics and log-transformed sums of serum PCDDs, PCDFs, PCBs, and TEQ and used logistic regression to determine the extent these metrics predicted high (top quartile) serum levels.Results: Overall, 16%, 30%, and 53% of participants lived within 3, 5, or 10km of one or more facility, respectively. No consistent associations were observed between serum levels and simple proximity metrics reflecting distance to nearest facility. Mean serum concentrations of total PCDDs/PCDFs/PCBs and total TEQ were highest among participants in the top AEI5k quartile; an increasing trend was statistically significant only for PCBs (p<0.01). In adjusted models, participants in the highest AEI5k quartile had increased odds of having high levels of total PCBs (OR=1.8; 95%CI:1.3-2.5) and TEQ (OR=1.6; 95%CI:1.0-2.5) compared to those with no facilities within 5km.Conclusion: In this nationally representative population, we demonstrated that residential proximity to emissions was positively associated with serum total PCBs and TEQ. Findings from this effort support the use of distance- and emissions-based exposure proxies to estimate personal exposure.

Screening Risk Assessment of Agricultural Areas under a High Level of Anthropopressure Based on Chemical Indexes and VIS-NIR Spectroscopy.

Intensive anthropogenic activity may result in uncontrolled release of various pollutants that ultimately accumulate in soils and may adversely affect ecosystems and human health. Hazard screening, prioritisation and subsequent risk assessment are usually performed on a chemical-by-chemical basis and need expensive and time-consuming methods. Therefore, there is a need to look for fast and reliable methods of risk assessment and contamination prediction in soils. One promising technique in this regard is visible and near infrared (VIS-NIR) spectroscopy. The aim of the study was to evaluate potential environmental risk in soils subjected to high level of anthropopressure using VIS-NIR spectroscopy and to calculate several risk indexes for both individual polycyclic aromatic hydrocarbons (PAHs) and their mixture. Results showed that regarding 16PAH concentration, 78% of soil samples were contaminated. Risk assessment using the most conservative approach based on hazard quotients (HQ) for 10 individual PAHs allowed to conclude that 62% of the study area needs further action. Application of concentration addition or response addition models for 16PAHs mixture gave a more realistic assessment and indicates unacceptable risk in 23% and 55% of soils according to toxic units (TUm) and toxic pressure (TPm) approach. Toxic equivalency quotients (TEQ) were below the safe limit for human health protection in 88% of samples from study region. We present here the first attempt at predicting risk indexes using VIS-NIR spectroscopy. The best results were obtained with binary models. The accuracy of binary model can be ordered as follows: TPm (71.6%) < HI (85.1%) < TUm (87.9%) and TEQ (94.6%). Both chemical indexes and VIS-NIR can be successfully applied for first-tier risk assessment.

Impact of transport of fine and ultrafine particles from open biomass burning on air quality during 2019 Bangkok haze episode

Transboundary and domestic aerosol transport during 2018–2019 affecting Bangkok air quality has been investigated. Physicochemical characteristics of size-segregated ambient particles down to nano-particles collected during 2017 non-haze and 2018–2019 haze periods were analyzed. The average PM2.5 concentrations at KU and KMUTNB sites in Bangkok, Thailand during the haze periods were about 4 times higher than in non-haze periods. The highest average organic carbon and elemental carbon concentrations were 4.6 ± 2.1 µg/m3 and 1.0 ± 0.4 µg/m3, respectively, in PM0.5–1.0 range at KU site. The values of OC/EC and char-EC/soot-EC ratios in accumulation mode particles suggested the significant influence of biomass burning, while the nuclei and coarse mode particles were from mixed sources. PAH concentrations during 2018–2019 haze period at KU and KMUTNB were 3.4 ± 0.9 ng/m3 and 1.8 ± 0.2 ng/m3, respectively. The PAH diagnostic ratio of PM2.5 also suggested the main contributions were from biomass combustion. This is supported by the 48-hrs backward trajectory simulation. The higher PM2.5 concentrations during 2018–2019 haze period are also associated with the meteorological conditions that induce thermal inversions and weak winds in the morning and evening. Average values of benzo(a)pyrene toxic equivalency quotient during haze period were about 3–6 times higher than during non-haze period. This should raise a concern of potential human health risk in Bangkok and vicinity exposing to fine and ultrafine particulate matters in addition to regular exposure to traffic emission.

Isolating different natural and anthropogenic PAHs in the sediments from the northern Bering-Chukchi margin: Implications for transport processes in a warming Arctic

Polycyclic aromatic hydrocarbons (PAHs) have become the dominating burden in the Arctic ecosystems, but their transport pathways and relative importance of different sources in the Arctic remained unclear, and this would be further complicated by climate change. Here we interpreted 27 PAHs in 34 surface sediments from the northern Bering-Chukchi margin. We integrated source apportionment methods (including diagnostic ratios, principal component analysis, hierarchical analysis, and positive matrix factorization (PMF) model) together with geochemistry parameters, which reveal a gradually clear picture of the spatial patterns of different sources. The total PAH concentrations (50.4 to 896.0 ng/g dw) exhibited a “hilly” shape with the increase of latitude, showing the highest level of PAHs in the northeast Chukchi Sea. The total BaP toxic equivalent quotient (TEQ) for carcinogenic compounds was from 1.06 to 33.3 ng TEQ/g. Most PAHs showed positive correlations with silt content, total organic carbon, stable carbon isotopes and black carbon (p < 0.01 or 0.05). Generally, source apportionment methods revealed an increasing petrogenic source of PAHs with latitudes. The PMF model further differentiated two petrogenic (36.7%), two pyrogenic (softwood and fossil fuel combustion, 35.5%) and one in-situ biogenic source (Perylene, 27.8%). An extremely high petrogenic signal was captured in the Canada Basin margin, possibly originating from the Mackenzie River via ice drifting with Beaufort Gyre, while another petrogenic source may come from coal deposit erosion by deglaciation. Softwood combustion (characterized by Retene) exhibited exclusively higher contribution in the northeast Chukchi Sea and might result from the increasing wildfire in Alaska due to climate change, whereas fossil fuel combustion exhibited similar contributions across different latitudes. Our results revealed natural PAHs as important “inside sources” in the Arctic, which are highly sensitive to global warming and deserves more attention.

Concentrations, distributions, sources, and risk assessment of polycyclic aromatic hydrocarbons in topsoils around a petrochemical industrial area in Algiers (Algeria)

Fifty-five samples were collected from topsoils around a petrochemical industrial area at the east of Algiers (Algeria) and analyzed for 16EPA priority PAHs in the aim to determine the concentrations, the distributions, and the possible sources of polycyclic aromatic hydrocarbons (PAHs). The results of the quantification are then devoted to the assessment of the potential risks as the toxicity, the risk for the ecosystem, and the risk for the human health. The sampling sites were classified into four categories: rural, suburban, urban, and industrial-urban. A new extraction method based on the insertion of a preliminary step, using hot water, was proposed to improve the extraction efficiency. Principal component analysis (PCA) and selected diagnostic ratio of PAHs were used to investigate the source apportionment of these PAHs. The potential toxicity, the ecological, and human health risk of PAHs in soil were estimated using the toxic equivalent quotient, the risk quotient, and the total lifetime cancer risk (TLCR) methods, respectively. The proposed new protocol gave improved recovery rates for the sixteen EPA PAHs particularly for low molecular weight PAHs, with satisfactory repeatability (RSD < 10%). The Σ16PAHs concentrations were varied from 143.73 to 4575.65μgkg-1 with a mean value of 1209.56μgkg-1. Σ16PAH concentrations found for the industrial areas would be 2 times higher than for urban soils and 3 times higher than for the rural soils. The biplots of PCA and the five diagnostic ratios suggested that the most sources of PAHs in the rural, the suburban, and the urban areas are traffic emissions, biomass burning, and coal combustion sources. Some points of the urban-industrial area are from the petroleum source. The found Σ16PAH concentrations and theirs calculated TEQs showed the following trend: industrial-urban > urban > suburban >rural. The potential cancer of human health risks calculated through TLCR results indicated that the exposure to the 7EPA PAH-contaminated soils produces negligible cancer risk to human health.

Physicochemical and toxicological characteristics of nanoparticles in aerosols in southern Thailand during recent haze episodes in lower southeast Asia

Transboundary haze from biomass burning is one of the most important air pollutions in Southeast Asia. The most recent serious haze episode occurred in 2015. Southern Thailand was affected by the haze during September to October when the particulate matter concentration hit a record high. We investigated physical and chemical characteristics of aerosols, including concentration and aerosol size distribution down to sub-micron sizes during haze episodes in 2013 and 2015 and, for reference, an insignificant haze period in 2017. The highest total suspended particulates and PM10 levels in Hat Yai city were 340.1 and 322.5 µg/m3. The mass fractions were nanoparticles (< 100 nm) 3.1%-14.8% and fine particles (< 1 µm) 54.6%-59.1%. Polycyclic aromatic hydrocarbon size distributions in haze periods peaked at 0.75 µm and the concentrations are 2-30 times higher than the normal period. High molecular weight (4-6 ring) PAHs during the haze episode contribute to about 56.7%-88.0% for nanoparticles. The average values of benzo(a)pyrene toxic equivalency quotient were 3.34±2.54ng/m3 in the 2015 haze period but only 0.89±0.17 ng/m3 in 2017. It is clear that particles smaller than 1 µm, were highly toxic. Nanoparticles contributed 19.4%-26.0% of total BaP-TEQ, whereas the mass fraction is 13.1%-14.8%. Thus the nanoparticles were more carcinogenic and can cause greater health effect than larger particles. The fraction of BaP-TEQ for nanoparticles during 2017 non-haze period was nearly the same, while the mass fraction was lower. This indicates that nanoparticles are the significant source of carcinogenic aerosols both during haze and non-haze periods.

Residential proximity to dioxin-emitting facilities and risk of non-Hodgkin lymphoma in the NIH-AARP Diet and Health Study

TPS 761: Health effects of pollution sources and components, Johan Friso Foyer, Floor 1, August 28, 2019, 3:00 PM - 4:30 PM Background: Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are persistent organic pollutants emitted from industrial combustion facilities and various manufacturing processes. Residential proximity to facilities emitting PCDD/Fs has been associated with increased PCDD/F levels in homes and risk of non-Hodgkin lymphoma (NHL), though few studies have investigated these relationships. Methods: We evaluated associations between residential proximity to dioxin-emitting facilities and NHL among participants of the NIH-AARP Diet and Health Study, a prospective cohort (N=548,845) in 6 states and 2 cities in the U.S. We linked geocoded enrollment addresses (1995-1996) with a U.S. Environmental Protection Agency database of 4,478 historical PCDD/F sources, which contained toxic equivalency quotient (TEQ) emissions estimates from 1995. We evaluated NHL risk with proximity metrics indicating presence/absence of one or more facilities within 3 or 5-km of participant homes, overall and separately by facility type (e.g. coal-fired power plants, municipal solid waste incinerators). We also examined risk by exposure intensity within 5km using a distance- and toxicity-weighted average emissions index (AEI [ng TEQ/km2]). Cox regression was used to estimate associations (hazard ratio, HR; 95% confidence interval, 95%CI) with NHL and major subtypes, adjusting for demographic, lifestyle, and dietary characteristics. Results: With 6,747 incident cases through 2011, we found no associations between overall or facility-specific PCDD/F proximity metrics and risk of NHL or major subtypes. However, participants with an AEI >95th percentile had significantly increased risk of developing NHL compared to unexposed participants (HR=1.27; 95%CI=1.05-1.53; p-trend=0.01). Risk of follicular lymphoma was also significantly elevated among participants with the highest quartile of the AEI (HR=1.33; 95%CI=1.02-1.74; p-trend=0.04). We saw no significant associations with other NHL subtypes. Conclusions: Using exposure metrics that accounted for distance and the toxicity of emissions, we found evidence of an association between residential exposure to high PCDD/F and risk of NHL overall and follicular lymphoma in particular.

Source Apportionment of Polychlorinated Biphenyls in Atmospheric Deposition in the Seattle, WA, USA Area Measured with Method 1668.

Atmospheric deposition can be an important pathway for the delivery of toxic polychlorinated biphenyls (PCBs) to ecosystems, especially in remote areas. Determining the sources of atmospheric PCBs can be difficult, because PCBs may travel long distances to reach the monitoring location, allowing for a variety of weathering processes that may alter PCB fingerprints. Previous efforts to determine the sources of atmospheric PCBs have been hampered by the electron capture detection methods used to measure PCBs. In this work, EPA method 1668, which is capable of measuring all 209 congeners, was used to measure PCBs in bulk atmospheric deposition at seven locations in the Green-Duwamish River watershed in and near Seattle, WA. Analysis of this data set via Positive Matrix Factorization allowed the identification of six factors that represent PCB sources. Four factors, representing approximately 88% of all PCB mass, are strikingly similar to unweathered Aroclors, suggesting minimal weathering during transport and/or local PCB sources at some sites. A fifth factor contained virtually all of the PCB 11 mass and represents PCBs from pigments. It explained approximately 39% of the Toxic Equivalency Quotient in the atmospheric deposition samples. The remaining factor contained non-Aroclor PCBs and may be related to silicone.

Characterization and health risk assessment of PM2.5-bound polycyclic aromatic hydrocarbons in 5 urban cities of Zhejiang Province, China

In 2015, we measured polycyclic aromatic hydrocarbons (PAHs) in atmospheric fine particulate matter (PM2.5) collected from 5 cities in Zhejiang Province. The mean toxic equivalent quotient (TEQ) values of benzo(a)pyrene (BaP) ranged between 1.2–3.1 ng/m3. The BaP-TEQ displayed seasonal trends, such that winter > spring and autumn > summer. During the winter, the most abundant individual PAHs were 4–6ring PAHs (84.04–91.65%). The median daily intake of atmospheric PAHs ranged between 2.0–7.4 ng/day for all populations, with seasonal trends identical to that of BaP-TEQ. The 95th incremental lifetime cancer risk (ILCR) values induced by PM2.5-bound PAHs were far lower than 10−6 for all populations. The data suggested that the pollution levels in the 5 Zhejiang Province cities were higher than the Chinese National Ambient Air Quality Standard (NAAQS). In the future, relevant measures should be taken to control atmospheric PAHs, especially 4–6 ring PAHs. The data also revealed no obvious cancer risk for populations residing in these 5 cities of Zhejiang Province.

Identification of the highest potential human health and environmental hazard in contaminated sediment near the point sources in the northwest Persian Gulf

The overall goal of this work was to determine the concentration levels and the potential ecological risks of 30 polycyclic aromatic hydrocarbons in the Persian Gulf sediments, Iran. The study also predicted the bioaccumulation of PAHs using the Monte Carlo simulation. For these goals, 68 surface sediment samples were collected from the Persian Gulf in January 2017. Then, the experiments were performed with Soxhlet system, chromatographic column and GC-MS instrument. According to the Canadian Sediment Quality Guidelines, 35.29% of sampling sites exhibited high potential adverse biological effects and 79.41% of samples have a low probability of toxicity. The mean bioaccumulated concentrations of carcinogenic PAHs in the Persian Gulf were predicted as 207.78 ± 262.23, 116.06 ± 146.47 and 69.26 ± 87.41 ng g–1 for mollusks, shrimps and crabs, respectively. The mean Toxic Equivalency and Mutagenic Equivalent Quotient for sediments was 702.06 ± 1012.37 and 500.37 ± 665.71 ng g−1, respectively. The 95th percentile carcinogenic and non-carcinogenic risks calculated for children and adults were lower than the threshold values of 10−6 and 1.0, respectively, revealing no potential health risk. The highest potential risks for toxicity were observed at sampling sites close to the Nowruz oil field and Mahshahr petrochemical economic zone based on the highest TEQcarc and MEQcarc values in this area.

Application of biochar to soils may result in plant contamination and human cancer risk due to exposure of polycyclic aromatic hydrocarbons

Biochars are added to soil to improve agronomic yield. This greenhouse- and field-scale study evaluated polycyclic aromatic hydrocarbon (PAH) contamination in 35 commercial and laboratory-produced biochars, and assessed the effects of biochar amendment of soils on PAH accumulation in vegetables and the risk for cancer. The total and bioavailable PAH concentrations in biochars varied from 638 to 12,347 μg/kg and from below the detection limit (BDL) to 2792 μg/kg, respectively. PAH formation in biochars decreased with increasing production temperature (350–650 °C). Root exudates enhanced PAH release from biochars. The total PAH concentrations in eight edible vegetables growing in biochar-amended soil varied according to biochar and vegetables type from BDL to 565 μg/kg. A health risk assessment framework was integrated with the benzo[a]pyrene toxic equivalency quotient and the incremental lifetime cancer risk (ILCR) to estimate the exposure risk for human beings via ingestion of PAH-contaminated vegetables. The total ILCR for adults was above 10−6, which suggests a risk to human health from direct exposure to PAHs in vegetables grown in biochar-amended soil. These results demonstrate that biochar application may lead to contamination of plants with PAHs, which represents a risk to human health. The PAH levels in biochars produced using different conditions and/or feedstocks need to be evaluated and biochars should be pretreated to remove PAHs before their large-scale agronomic application.

Assessment of Polychlorinated Biphenyls (PCBs) in water, sediments and biota from e-waste dumpsites in Lagos and Osun States, South-West, Nigeria

The levels of PCBs in sediments, water, leachate and aquatic fauna ( Tilapia guineensis , Callinectes amnicola and Cardiosoma armatum ) found in and around e-waste dumpsites in Lagos and Osun States, South-West, Nigeria were analyzed using Gas Chromatography Electron Capture Detector (GC ECD) Agilent 7820A. All the 28 PCBs congeners studied were detected with the Σhexa-PCBs dominating in Lagos (21%) while the Σtetra-PCBs (24%) enriched the samples from Osun State. The concentrations of Σ- PCBs in decreasing order were Lagos: sediment ˃ fish gill ˃ fish muscles ˃ water ˃ crab ˃ leachate and Osun: fish gill ˃ fish muscle ˃ sediment ˃ crab ˃ water ˃ leachate. The concentrations of total indicator PCBs ( Σ7PCBs) in the sediment from Lagos (4.19 μg/kg) and Osun (8.58 μg/kg) exceeded the Canadian Sediment Quality standard threshold effect level (CSQ TEL) (0.03 μg/kg) and the National Oceanic Atmospheric Administration threshold effect level (NOAA TEL) for fresh and marine sediments.. The calculated toxic equivalent quotient (TEQ) for fish from Lagos and Osun (3.7 and 4.4) respectively further suggests a likely occurrence of adverse effects to humans who consume the fish. This study reveals the high health and ecological risks associated with e waste pollution in the aquatic environment. Keywords: e-waste, polychlorinated Biphenyls, aquatic environment, leachate

Risk Assessment of Emitted Particle-bound Polycyclic Aromatic Hydrocarbons from Lignite-biomass Pelletization Burning: Size Distribution and Human Health Effects

Risk assessment of emitted particle polycyclic aromatic hydrocarbons (PAHs) from lignite-biomass pelletization burning focusing on size distribution and human health effects are investigated. The particles and PAHs are experimented by a tube furnace and high performance liquid chromatography coupled diode array and fluorescence detectors (HPLC-DAD/FLD), respectively. The carcinogenic, mutagenic, and toxic potencies of PAHs are also discussed in relative to the size distribution of emitted particle PAHs. The results indicate that the carcinogenic, mutagenic, and toxic potencies of PAHs are like to accumulate in the ultrafine particles finer than 0.65 µm. The ultrafine particles contribute the largest PAHs existences of carcinogenic, mutagenic and toxic substances; even though they register in the small mass fraction of PAHs. Moreover, the co-pellets burning can reduce the values of carcinogenic PAHs, carcinogenic equivalency quotients (BaP-TEQ), mutagenic equivalency quotients (BaP-MEQ), and toxic equivalency quotients (TCDD-TEQ) by more than 60%.

Distribution, source apportionment and health risk assessment of polycyclic aromatic hydrocarbons (PAHs) in intertidal sediment of Asaluyeh, Persian Gulf.

Surface sediment samples were collected from intertidal zone of Asaluyeh, Persian Gulf, to investigate distribution, sources and health risk of sixteen polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations ranged from 1.8 to 81.2μgkg-1 dry weight, which can be categorized as low level of pollution. Qualitative and quantitative assessments showed that PAHs originated from both petrogenic and pyrogenic sources with slight pyrogenic dominance. Source apportionment using principal component analysis indicated that the main sources of PAHs were fossil fuel combustion (33.59%), traffic-related PAHs (32.77%), biomass and coal combustion (18.54%) and petrogenic PAHs (9.31%). According to the results from the sediment quality guidelines, mean effects range-median quotient (M-ERM-Q) and benzo[a]pyrene toxic equivalents (BaPeq), low negative ecological risks related to PAH compounds would occur in the intertidal zone of Asaluyeh. The total benzo[a]pyrene (BaP) toxic equivalent quotient (TEQcarc) for carcinogenic compounds ranged from 0.01 to 7μgkg-1-BaPeq, indicating low carcinogenic risk. The human health risk assessment of PAH compounds via ingestion and dermal pathways suggests low and moderate potential risk to human health, respectively.

Appraisement, source apportionment and health risk of polycyclic aromatic hydrocarbons (PAHs) in vehicle-wash wastewater, Pakistan

Vehicle-wash wastewater (VWW) contains elevated concentrations of different petrochemicals including polycyclic aromatic hydrocarbons (PAHs), a carcinogenic group of organic compounds. This study investigates the discharge of PAHs present in the untreated wastewater of vehicle-wash stations (VWS) located in district Peshawar, Pakistan. The data obtained was being novel with the detection of 16 USEPA PAHs (both individuals and total) and compared with earlier studies and international standards. The ∑16PAHs in wastewater from light vehicle-wash stations (LVWS) and heavy vehicle-wash stations (HVWS) ranged from 245–429μg/l and 957–1582μg/l, respectively. A significant difference (p<0.01) was observed in PAHs discharged from LVWS and HVWS. The projected ∑16PAHs discharge from both HVWS (92% of total generated PAHs) and LVWS (8%) was about 5109.9 g per annum. According to PAH diagnostic ratios, PAHs were both petrogenic (chrysene/benz(a)anthracene, low molecular weight/high molecular weight) and pyrogenic (phenanthrene/anthracene, fluoranthene/pyrene, fluoranthene/fluoranthene+pyrene) in origin. The highest toxic equivalent quotient (TEQ) value was shown by benzo(a)pyrene (21.6μg/l) followed by dibenz(ah)anthracene (9.81μg/l) in wastewater from HVWS. However, in LVWS the case was reversed with highest value (7.54μg/l) for dibenz(ah)anthracene followed by benzo(a)pyrene (3.54μg/l). The lowest TEQ value was indicated for phenanthrene (0.007μg/l) in wastewater of LVWS, while pyrene showed the lowest value (0.007μg/l) in wastewater of HVWS. The results indicated that VWS contribute significant amount of PAHs each year, which is of great concern regarding water quality, ecological and human health risk. This is the first systematic and comprehensive research related with generation of PAHs load per day, week, month and annum from VWS, their source apportionment and health effects in Pakistan.

Chlorinated polycyclic aromatic hydrocarbons in surface sediment from Maowei Sea, Guangxi, China: occurrence, distribution, and source apportionment.

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) with three to five aromatic rings have been documented to ubiquitously occur in environmental matrices. In this study, residual concentrations and profiles of 20 individual ClPAHs were determined in 35 surface sediment samples from Maowei Sea, a semi-enclosed shallow inland bay located in the northwestern part of South China Sea. The concentrations of ΣClPAHs in sediment ranged from 313 to 9650pg/g dw with a detection rate of 43-100%. Of the individual ClPAH congeners, 9-ClPhe was the most abundant in Maowei Sea with the concentrations that ranged from 99.9 to 3610pg/g dw (mean 1120pg/g dw). High-molecular-weight ClPAH congeners (four to five rings) were predominant in sediments from sampling locations near a petrochemical industrial complex, whereas low-molecular-weight ClPAH congeners (three rings) were predominant in sediments from estuarine and mangrove locations. A positive matrix factorization (PMF) model in combination with dioxin-like toxic equivalency quotient (TEQ) results was used to apportion sources of ClPAHs. Vehicular emission, combustion/chemical industrial processes, and two other unknown sources accounted for 40.1, 25.5, 20.8, and 13.6%, respectively, of ClPAH sources in sediment; their contribution to TEQs in sediments were 24.2, 40.5, 19.3, and 16.0%, respectively. Further investigations are needed to elucidate potential sources and ecological risks of ClPAHs in sediments.

Polycyclic aromatic hydrocarbons (PAHs) at the Gulf of Kutch, Gujarat, India: Occurrence, source apportionment, and toxicity of PAHs as an emerging issue

The present study extrapolates the assessment and characterization of a barely studied region, the Gulf of Kutch, (near Jamnagar), Gujarat, India, in terms of PAH exposure, adverse effects caused by them, and various toxicological indices showing the catastrophic effects of their elevated concentrations. ΣPAH concentration in the site ranged from 118,280 to 1,099,410ngg−1 dw, with a predominance of 2–3-ring PAHs (79.09%) as compared to 4–5- and 6-ring PAHs (20.91%). The concentrations of carcinogenic PAHs were found to be between 8120 and 160,000ngg−1 dw, with a mean of 63,810ngg−1 dw, which is much higher than normal acceptable values. The toxic equivalent quotient for 6CPAHs ranged from 150.47 to 26,330ngg−1 BaPeq, encompassing 50.63% of ΣPAH toxicity. This toxicological profile of the present study site would be of paramount importance as it offers fresh information regarding the load of legacy pollutants such as PAHs and the inputs and methods to cope with their extremely high concentrations in less explored marine habitats.

Phenyltrichlorosilane-functionalized magnesium oxide microspheres: Preparation, characterization and application for the selective extraction of dioxin-like polycyclic aromatic hydrocarbons in soils with matrix solid-phase dispersion

Magnesium oxide microspheres functionalized with phenyltrichlorosilane (PTS-MgO) were synthesized by surface modification through silanization reaction, which was confirmed by Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetry analysis (TGA) and N2 adsorption-desorption. The result indicated that PTS-MgO not only possessed the ability of enhancing the retention with PAHs, but also weakening the interference from chlorinated compounds. As a sorbent for the matrix solid-phase dispersion (MSPD) extraction, PTS-MgO was used to selectively extract seven dioxin-like polycyclic aromatic hydrocarbons (DL-PAHs) from soil samples. Various parameters affecting the recoveries of seven DL-PAHs were investigated and optimized, such as sorbent/sample mass ratio, grinding time, rinsing and eluting conditions. Under the optimized conditions, the developed method combining MSPD with HPLC-FLD exhibited good sensitivity (0.02–0.12 ng g−1 detection of limits) and linearity (linear correlation coefficient greater than 0.9997). Satisfactory recoveries with DL-PAHs spiked at two levels (10 and 80 ng g−1) were obtained in the range of 72.2–113.1% with RSD < 9.6%, indicating that PTS-MgO had a potential in MSPD extraction of DL-PAHs in soils. Additionally, the proposed MSPD-HPLC-FLD method was also verified by detecting seven DL-PAHs in the standard reference soil. Based on the developed method, DL-PAHs in soil samples were detected with the concentration ranging from 70.08 to 555.05 ng g−1 dry weight (dw). The total toxic equivalency quotients (TEQ) of seven DL-PAHs varied from 9.93 to 143.94 ng TEQ/g dw.

Automated milk fat extraction for the analyses of persistent organic pollutants.

We have utilized an automated acid hydrolysis technology, followed by an abbreviated Soxhlet extraction technique to obtain fat from whole milk for the determination of persistent organic pollutants, namely polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls. The process simply involves (1) pouring the liquid milk into the hydrolysis beaker with reagents and standards, (2) drying the obtained fat on a filter paper and (3) obtaining pure fat via the modified Soxhlet extraction using 100mL of hexane per sample. This technique is in contrast to traditional manually intense liquid-liquid extractions and avoids the preparatory step of freeze-drying the samples for pressurized liquid extractions. Along with these extraction improvements, analytical results closely agree between the methods, thus no quality has been compromised. The native spike (n=12) and internal standard (n=24) precision and accuracy results are within EPA Methods 1613 and 1668 limits. While the median (n=6) Toxic Equivalency Quotient (TEQ) for polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans and the concentration of the marker polychlorinated biphenyls show a percent difference of 1% and 12%, respectively, compared to 315 previously analyzed milk samples at the same laboratory using liquid-liquid extraction. During our feasibility studies, both egg and fish tissue show substantial promise using this technique as well.