Spatial variation of PAHs and PCBs in coastal air, seawater, and sediments in a heavily industrialized region.

Concurrent coastal seawater (n = 22), sediment (n = 22), and atmospheric samples (n = 10) were collected in the Aliaga industrial region, Turkey, to explore the spatial variation, sources, and air-seawater exchange of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Seawater Σ16PAH concentrations (particle + dissolved) ranged between 5107 and 294,624 pg L-1, while Σ41PCB concentrations were in the range of 880-50,829 pg L-1. Levels in sediments were highly variable ranging between 35.5-49,682 and 2.7-2450 µg kg-1 in dry weight for Σ16PAHs and Σ41PCBs, respectively. Atmospheric concentrations varied between 1791-274,974 and 104-20,083 pg m-3 for Σ16PAHs and Σ41PCBs, respectively. Sediment organic matter (OM) content and levels of Σ16PAHs and Σ41PCBs correlated weakly (r 2 = 0.19-0.23, p < 0.05) suggesting that the spatial variations of PAHs and PCBs were mainly affected by local sources rather than their sorption to OM. The geographical distribution of PAH and PCB concentrations in air, seawater, and sediment and factor analysis on the sediment levels pointed out that the major sources in the region are steel plants, petroleum refinery, petrochemical complex, ship breaking, loading/unloading activities at the ports, vehicular emissions, and fossil fuel combustion emissions. The direction of the air-seawater exchange was also explored by estimating seawater fugacity fractions of PAHs and PCBs. For PAHs, the number of cases implying deposition (43.0%) and volatilization (39.5%) was similar, while for PCBs, the number of cases implying volatilization (60.4%) was much higher compared to deposition (21.6%). Fugacity fractions were generally <0.36 (deposition) at the sites close to industrial and ship breaking activities where the highest seawater and sediment levels were measured, implying that atmospheric deposition is an important mechanism affecting seawater and sediment PAH and PCB levels.

Polychlorinated naphthalene (PCN) emissions from scrap processing steel plants with electric-arc furnaces.

Polychlorinated naphthalene (PCN) emissions of scrap iron processing steel plants were explored by measuring concentrations in stack gases of five plants, in the atmosphere (n=11) at a site close to those plants, and in soil at several sites in the region (n=40) in Aliaga, Izmir, Turkey. Observed stack-gas Σ32PCN levels from the plants without scrap preheating (189±157ngNm-3, average±SD, n=4) showed that they are substantial PCN emitting sources. Stack-gas Σ32PCN level for the plant with scrap preheating was considerably higher (1262ngNm-3). Similarly, Σ32PCN emission factor for this plant was substantially higher (11.9mgton-1) compared to those without scrap preheating (1.30±0.98mgton-1). Results have also suggested that the investigated steel plants emit large quantities of fugitive particle-phase PCNs. Measured soil Σ32PCN concentrations that are considered to be representative of the atmospheric levels were greatly variable in the region, ranging between 0.003 and 10.02µgkg-1 (dry wt). Their spatial distribution showed that main PCN sources in the region were the iron-steel plants. Ambient air levels (1620±800pgm-3) were substantially higher than ones observed around the world and in the study area verifying that the steel plants with electric arc furnaces (EAFs) are important PCN sources. Investigation of possible mechanisms suggested that the combustion processes also contribute to emissions from EAFs in addition to evaporation of PCNs present in the scrap iron.

Investigation of spatial distributions and sources of persistent organic pollutants (POPs) in a heavily polluted industrial region using tree components.

Spatial distributions of persistent organic pollutants (POPs) were investigated in Iskenderun industrial region in Turkey. POP concentrations were measured in different tree components (i.e., pine needle, branch, bark, and stem) collected at several industrial and background sites (n = 27). Also, air, litter, and soil samples were analyzed to determine the relationship of atmospheric pollutants with tree components, litter, and soil. Spatial variation of measured concentrations and factor analysis showed that the iron-steel plants are the most important POP sources in Iskenderun area. Correlations of ambient air levels to those measured in soil, litter, and tree components were significant showing that POPs are exchanged between atmosphere and these compartments. Results have suggested that tree components, litter and soil could be used to determine the spatial distributions and sources of atmospheric POPs in a region. POP quantities (mg/ha) accumulated in different tree components, litter, and soil were also predicted. Generally, the highest quantities were accumulated by stem and needles. In terms of overall inventory, including trees, litter and soil, the highest accumulated quantities were found in soil followed by trees and litter, indicating that in addition to soil, vegetation is a notable reservoir accumulating POPs. Ambient air POP concentrations were also estimated using a bark/air partitioning model. The estimated/measured ratios were close to 1.0 for several compounds and the results showed that the atmospheric POP concentrations could be estimated from the bark measurements within factors of 0.23-3.07, 1.02-6.67, 0.63-7.44, 1.07-3.37 for polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polychlorinated naphthalenes, and polybrominated diphenyl ethers, respectively.

Investigation of spatial and historical variations of air pollution around an industrial region using trace and macro elements in tree components.

Several trace and macro elements (n=48) were measured in pine needle, branch, bark, tree ring, litter, and soil samples collected at 27 sites (21 industrial, 6 background) to investigate their spatial and historical variation in Aliaga industrial region in Turkey. Concentrations generally decreased with distance from the sources and the lowest ones were measured at background sites far from major sources. Spatial distribution of anthropogenic trace elements indicated that their major sources in the region are the iron-steel plants, ship-breaking activities and the petroleum refinery. Patterns of 40 elements that were detected in most of the samples were also evaluated to assess their suitability for investigation of historical variations. Observed increasing trends of several trace and macro elements (As, Cr, Fe, Mo, Ni, V, Cu, Pb, Sb, Sn, and Hg) in the tree-ring samples were representative for the variations in anthropogenic emissions and resulting atmospheric concentrations in Aliaga region. It was shown that lanthanides (La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb) could also be used for the investigation of historical variations due to specific industrial emissions (i.e., petroleum refining). Results of the present study showed that tree components, litter, and soil could be used to determine the spatial variations of atmospheric pollution in a region while tree rings could be used to assess the historical variations.

Biomonitoring the spatial and historical variations of persistent organic pollutants (POPs) in an industrial region.

Several persistent organic pollutants (POPs) like polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and polybrominated diphenyl ethers (PBDEs) were measured in needle, branch, bark, and tree ring samples in pine samples collected at 27 sites (21 industrial, 6 background) in Aliaga industrial region in Turkey. Soil, litter, and air samples were also collected to investigate the relationships between the air and soil, litter, and tree components. Concentrations decreased with distance from the sources and the lowest ones were measured at background sites. The spatial distribution of POPs indicated that the major sources in the region are the iron-steel, ship-breaking, petrochemical plants and the petroleum refinery. Significant correlations between the air concentrations and, soil, litter, and tree components indicated the interaction of these compartments with air. Observed increasing trends of POPs in the tree-ring samples were representative for the variations in anthropogenic emissions and resulting atmospheric concentrations in Aliaga region. These results indicated that tree components, litter and soil could be used to determine the spatial variations while tree rings could be used to investigate the historical trends of atmospheric POPs in a region. POP amounts (mg/ha) stored in different tree components, litter, and soil were also inventoried. Among the tree components, generally, the highest amounts were stored in the stem followed by needles. For the overall inventory, the highest amounts were stored in soil for PCNs, PBDEs, and PCBs while highest PAH amounts were stored in trees, indicating that in addition to soil, vegetation is also an important reservoir for POPs.

Biogenic volatile organic compound (BVOC) emissions from forested areas in Turkey: determination of specific emission rates for thirty-one tree species.

Normalized biogenic volatile organic compound (BVOC) emission rates for thirty one tree species that cover the 98% of national forested areas in Turkey were determined. Field samplings were performed at fourteen different forested areas in Turkey using a specific dynamic enclosure system. The selected branches of tree species were enclosed in a chamber consisted of a transparent Nalofan bag. The air-flows were sampled from both inlet and outlet of the chamber by Tenax-filled sorbent tubes during photosynthesis of trees under the presence of sunlight. Several environmental parameters (temperature, humidity, photosynthetically active radiation-PAR, and CO2) were continuously monitored inside and outside the enclosure chamber during the samplings. Collected samples were analyzed using a gas chromatography mass spectrometry (GC/MS) system equipped with a thermal desorber (TD). Sixty five BVOCs classified in five major groups (isoprene, monoterpenes, sesquiterpenes, oxygenated sesquiterpenes, and other oxygenated compounds) were analyzed. Emission rates were determined by normalization to standard conditions (1000 µmol/m(2)s PAR and 30 °C temperature for isoprene and 30 °C temperature for the remaining compounds). In agreement with the literature, isoprene was mostly emitted by broad-leaved trees while coniferous species mainly emitted monoterpenes. Several tree species such as Sweet Chestnut, Silver Lime, and European Alder had higher monoterpene emissions although they are broad-leaved species. High isoprene emissions were also observed for a few coniferous species such as Nordmann Fir and Oriental Spruce. The highest normalized total BVOC emission rate of 27.1 µg/gh was observed for Oriental Plane while South European Flowering Ash was the weakest BVOC emitter with a total normalized emission rate of 0.031 µg/gh. Monoterpene emissions of broad-leaved species mainly consisted of sabinene, limonene and trans-beta-ocimene, while alpha-pinene, beta-pinene and beta-myrcene were generally emitted by coniferous species. Oxygenated compounds were the third most prominent BVOC group and sesquiterpenes had slightly lower contributions.

Spatial distribution and source identification of trace elements in topsoil from heavily industrialized region, Aliaga, Turkey.

Topsoil samples (n = 40) were collected from a heavily industrialized region in Turkey. The region includes several scrap processing iron-steel plants with electric arc furnaces (EAFs), a petroleum refinery, a petrochemical complex, steel rolling mills, a natural gas-fired power plant, ship-breaking yards and very dense transportation activities. The region has undergone a rapid transition from an agricultural region to a heavily industrialized region in the last three decades. Collected soil samples were analyzed for 48 trace elements using inductively coupled plasma-mass spectrometry (ICP-MS). The elemental distribution pattern in the region indicated that Nemrut area with dense iron-steel production activities was a hotspot for elemental pollution. In addition to crustal elements, concentrations of anthropogenic trace elements (i.e., Fe, Zn, Pb, Mn, Cu, Cd, Cr and Mo) were very high in the area influencing many parts of the region. Elemental compositions of fugitive sources polluting the soil (i.e., paved and unpaved roads, slag piles, EAFs filter dust piles and coal piles) were also determined. The methods (enrichment factors [EFs] and the index of geoaccumulation [Igeo]) used for determination of pollution status of soil showed that Cr, Ag, Zn, As and Pb were the strongly contaminating elements for the region. Principal component analysis (PCA) clearly indicated that anthropogenic sources (steel production, refinery and petrochemical processes and traffic) were important sources in this region.

Electric arc furnaces for steel-making: hot spots for persistent organic pollutants.

Persistent organic pollutant (POP) concentrations were measured in stack-gases of ferrous scrap processing steel plants with electric arc furnaces (EAFs) (n = 5) in Aliaga, Izmir, Turkey and in air (n = 11) at a site near those plants. Measured stack-gas concentrations for the four plants without scrap preheating (611 +/- 311, 165,000 +/- 285,000, and 33 +/- 3 ng m(-3), average +/- SD for sigma41PCBs, sigma16PAHs, and sigma7PBDEs, respectively) indicated that they are significant sources for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). POP emissions from the plant with scrap preheating were significantly higher (13 500, 445 000, and 91 ng m(-3) for sigma41PCBs, sigma16PAHs, and sigma7PBDEs, respectively). It was also shown that the steel plants emit considerable amounts of fugitive POPs in particle-phase. Estimated emissions using the emission factors generated in this study and the production amounts suggested that the steel plants with EAFs may significantly contribute to local and global PAH, PCB, and PBDE emissions. Several other compounds (aromatic and aliphatic hydrocarbons, oxygen, sulfur, nitrogen, and chlorine-containing organic compounds, n = 49) were identified and determined semiquantitatively in the stack-gas and ambient air samples. Ambient air concentrations (62 +/- 35, 320 +/- 134 ng m(-3), 1451 +/- 954 pg m(-3), for sigma41PCBs, sigma16PAHs, and sigma7PBDEs, respectively) were significantly higher than those measured previously around the world and in the region, further confirming that the steel plants with EAFs are "hot spots" for POPs.