Basin scale monitoring of microplastics and phthalates in sediments from the Persian Gulf and the Gulf of Makran using GIS-based algorithms: Insights towards spatial variation and potential risk assessment.

Information on sedimentary microplastics and phthalates has been restricted to the coastal regions of the Persian Gulf and the Gulf of Makran. Our basin-wide study monitored their levels, spatial behaviors, and potential risks using GIS-based techniques. Microplastics and phthalates ranged from 5 to 75 particles/kg d.w and 0.004-1.219 µg g-1 d.w, respectively. Microplastics were in the size category of 100 µm to 3 mm, and black microfibers (< 1 mm) and high-density polymers were dominant. The total number of microplastics was between 356.333 × 1012 and 469.075 × 1012 particles in the surface sediments of the studied regions (confidence interval = 99 %). Diethylhexyl phthalate (DEHP) and Di-isobutyl phthalate contributed 88 % of detected phthalates. Significant correlations among microplastic abundance, total phthalates, and DEHP were distinguished (p < 0.05). Overall, the findings reiterated the widespread presence of microplastics and a potential link between phthalates and microplastics. Semi-variogram, cluster Voronoi polygons, and Trend analysis identified spatial outliers and major deposition sites of microplastics and phthalates and consequently outlined the localities where upcoming studies should be concentrated. A hotspot of potential risks was marked using Fuzzy logic and GIS-based algorithms in the Sea of Makran, covering an area equal to 342. 99 km2.

Normal alkanes in sediments from the Persian Gulf: spatial pattern and implications for autochthonous, allochthonous, and petroleum-originated contaminants.

Surface sediments (n = 124) were gathered to evaluate spatial pattern and source apportionment of ∑24n-alkanes in the Persian Gulf. Moran's I indices revealed that ∑24n-alkanes were randomly distributed in sampling space in general. One noticeable exception was a significant spatial high-high cluster (Z-score = 8.6). Profile of n-alkanes observed for this cluster maximized at n-C20, n-C18, n-C16, and n-C22. Detection of very low carbon preference indices and strong even carbon-numbered predominance suggested that bacterial inputs were the process making this cluster. Based on diagnostic ratios and GIS techniques, in situ production of organic materials was widespread in the studied space. Allochthonous and petroleum-based inputs were not traceable for 73.8% and 24.7% of the area, respectively. Petrogenic source apportionment map proposed that petroleum-originated contaminants were probably limited to 6.32 km2 of the sampling matrix. The biogenic inputs (autochthonous and allochthonous inputs) and not the petroleum contaminants were the main source of n-alkanes deposited.

Using GIS, geostatistics and Fuzzy logic to study spatial structure of sedimentary total PAHs and potential eco-risks; An Eastern Persian Gulf case study.

GIS, geo-statistics and autocorrelation analysis were employed to reveal spatial structure of sedimentary ∑16PAHs. Global Moran's I index outlined significant ∑16PAHs clusters for the entire region (Moran's I index =0.62, Z-score = 25.6). Anselin Moran's I index specified locations of the significant low/high spatial clusters. The levels of random and structural variance of ∑16PAHs were about 0.083 and 0.154, respectively. Nugget to sill ratio confirmed that ∑16PAHs has a moderate level of spatial structure and the major part of PAHs variability is not random. Prediction and standard error maps of ∑16PAHs, produced by ordinary kriging, highlighted that more samples should be taken from high cluster region for next studies. Fuzzy logic functions (OR and AND) were used to develop eco-risk maps. It revealed that the potential hazards of PAHs are considerable at the vicinity of petrochemical facilities.

Spatial distribution and vertical profile of heavy metals in marine sediments around Iran's special economic energy zone; Arsenic as an enriched contaminant.

Surface sediments (n = 35) and a core sample around Pars Special Economic Energy Zone were analyzed to address spatiotemporal variations of heavy metals. Enrichment factors classified the elements as: (1) poorly enriched, geogenic elements (Co, Cr, Fe, Li, Mn, Mo, Ni, Ti, and V), (2) minimal enriched elements (Zn and Mg), (3) moderately enriched elements (Ag, Cd, Pb, Se, and Sr), and (4) significantly enriched element (As and Hg). The core profile showed that As, Hg, Ag, and Cd had considerable anthropogenic inventories. Arsenic levels were continuously increasing toward the top of the core and sedimentary cycling was not an effective factor on its enrichment. Pollution load index classified the area as a severely affected region and Risk Index values suggested that 57% of the sediments had a moderate potential risks. The mapping techniques proposed a polluted and hazardous patch at the entrance and center part of the Nayband Bay.

Origin, toxicological and narcotic potential of sedimentary PAHs and remarkable even/odd n-alkane predominance in Bushehr Peninsula, the Persian Gulf.

Surface sediments (n=17) were collected from 6 sites located in the coasts of the Bushehr Peninsula. ∑16PAH concentrations were in the range of 285.9-1288ngg-1 dw and the sediments were moderately polluted. Py, Ph, B(a)A and Flu showed >70% of the detected values in order of the mentioned rank. 4-ring PAHs were the dominant compounds and the molecular ratios presented the dominant pyrolytic source. The toxicity of PAHs for sediment dwelling life was averagely equivalent to occurrence of 0.08ngg-1 of Dioxin in dw of the examined sediments. The evaluated narcotic potential (confidence level of 99%) was 0.027-3.04 and upper part of the Bushehr Peninsula, where the human population is more concentrated, showed more narcotic potential. ∑n-alkane concentrations (n-C15-n-C32) were in the range of 3.10-35.6µgg-1 dw. The dominant distribution of even carbon number n-alkanes was traced back to a possibly autochthonous source.

Polytetrafluoroethylene physisorption-assisted emulsification microextraction as a cleanup and preconcentration step in the gas chromatography determination of aliphatic hydrocarbons in marine sediment samples.

For the first time, the application of polytetrafluoroethylene powder as an extractant phase collector or holder in liquid-phase microextraction has been developed. For this purpose, the analytical performances of two different ways of applying polytetrafluoroethylene powder in microextraction methods including polytetrafluoroethylene physisorption-assisted emulsification microextraction and dispersive liquid-phase microextraction via polytetrafluoroethylene extractant phase holders have been compared for analysis of aliphatic hydrocarbons in aqueous phases. Under the same conditions, the former showed better extraction efficiencies over the latter and as a result, it was applied as preconcentration and cleanup step in the analysis of aliphatic hydrocarbons in sediment samples followed by gas chromatography analysis. The linearity of the polytetrafluoroethylene physisorption-assisted emulsification microextraction method was obtained over a range of 3.7 and 2000 ng/g (R2 > 0.993). The relative standard deviations were less than 6.5% (n = 3). The limits of detection and quantification obtained by this method were 1.1-9.0 and 3.7-30 ng/g, respectively, indicating that satisfactory results were achieved by the procedure.

Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf.

In the present study, antifouling paint booster biocides, Irgarol 1051 and diuron were measured in ports and marinas of Bushehr, Iran. Results showed that in seawater samples taken from ports and marinas, Irgarol was found at the range of less than LOD to 63.4ngL(-1) and diuron was found to be at the range of less than LOD to 29.1ngL(-1) (in Jalali marina). 3,4-dichloroaniline (3,4-DCA), as a degradation product of diuron, was also analyzed and its maximum concentration was 390ngL(-1). Results for analysis of Irgarol 1051 in sediments showed a maximum concentration of 35.4ngg(-1) dry weight in Bandargah marina. A comparison between the results of this study and those of other published works showed that Irgarol and diuron pollutions in ports and marinas of Bushehr located in the Persian Gulf were less than the average of reports from other parts of the world.

Dissolved carbon dioxide flotation: an effective way for phase separation in emulsification microextraction method.

Dissolved carbon dioxide flotation after emulsification microextraction (DCF-EME) technique coupled with gas chromatography-electron capture detection (GC-ECD) was introduced for preconcentration and determination of six organochlorine pesticides (OCPs) in seawater samples. DCF-EME method is based on the rapid and simple phase separation of low density organic solvent from the aqueous phase via introducing of a saturated NaHCO3 solution (9.6% w/v) into the acidified sample solution (0.1M of HCl) containing analytes. Thanks to the in situ generation of carbon dioxide (CO2) bobbles intensified by ultrasound radiation, the dispersed extraction solvent was collected to the surface of the aqueous sample and then was narrowed to the capillary part of a special home-made extraction cell for facile retrieving. Under the optimal conditions, the limits of detection were at the range of 2.6-9.2 ng L(-1) and preconcentration factors were varied between 271 and 307 for different OCPs. The applicability of the developed method was evaluated by the extraction and determination of the target analytes from Caspian seawater samples.

Microfunnel-supported liquid-phase microextraction: application to extraction and determination of Irgarol 1051 and diuron in the Persian Gulf seawater samples.

In the present work, microfunnel-supported liquid-phase microextraction method (MF-LPME) based on applying low density organic solvent was developed for the determination of antifoulings (Irgarol 1051, diuron and 3,4-dichloroaniline) from seawater samples. In this method, home-designed MF device was used for facile loading and retrieving of organic solvent during the extraction procedure. The extraction was carried out with introduction of 400 µL of toluene via syringe into the MF device placed on the surface of sample solution (300 mL) containing analytes. After the extraction, extractant layer was narrowed into the capillary part of MF by pushing the device inside the sample and withdrawn by using a syringe to evaporate by nitrogen purging. The residual redissolved into 50 µL methanol, diluted to 100 µL with deionized water and injected into the high performance liquid chromatography with UV detection (HPLC-UV). Several factors influencing the extraction such as the type and volume of extraction solvent, sample pH, extraction time and ionic strength were investigated and optimized. Under the optimized conditions, the limits of detection in seawater were 1.4, 4.8 and 1.0 ng L(-1) for 3,4-dichloroaniline (DCA), diuron and Irgarol 1051, respectively. Enrichment factors were obtained 333, 150 and 373 for DCA, diuron and Irgarol 1051, respectively. The precision of the technique was evaluated in terms of repeatability which was less than 12.0% (n=5). The applicability of the proposed method was evaluated by the extraction and determination of antifoulings from seawater samples collected from harbors of Bushehr located in northern Persian Gulf coast.

Comparison of conventional hollow fiber based liquid phase microextraction and electromembrane extraction efficiencies for the extraction of ephedrine from biological fluids.

In the present study, hollow fiber liquid phase microextraction (HF-LPME) based on pH gradient and electromembrane extraction (EME) coupled with high-performance liquid chromatography (HPLC) was compared for the extraction of ephedrine from biological samples. The influences of fundamental parameters affecting the extraction efficiency of ephedrine were studied and optimized for both methods. Under the optimized conditions, preconcentration factors of 120 and 35 for urine and 51 and 8 for human plasma were obtained using EME and HF-LPME, respectively. The calibration curves showed good linearity for urine and plasma samples by both methods with the coefficient of estimations higher than 0.98. The limits of detection were obtained 5 and 10 ng mL(-1) using EME and 60 and 200 ng mL(-1) by HF-LPME for urine and plasma samples respectively. The relative standard deviations of the analysis were found in the range of 5.2-8.6% (n=3). The results showed that in comparison with HF-LPME based on pH gradient, EME is a much more effective transport process, providing high extraction efficiencies in very short time.