Atmospheric occurrence and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the open Mediterranean Sea.

The overall objective of this work is to provide the first evaluation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) occurrence and deposition to Mediterranean open seawater. sigma2,3,7,8-PCDD/F air (gas+aerosol) concentrations over the Mediterranean Sea ranged from 60 to 1040 fg m(-3). The highest value (1555 fg m(-3)) was measured in a reference sample taken in the SW Black Sea. No consistent trend regarding the diel cycle of PCDD/Fs was observed. PCDD/Fs transported to the open sea waters from continental areas and across the Atlantic as well as ship emissions may be significant sources to the open Mediterranean. Seawater concentrations in the Mediterranean ranged from 42 to 64 fg L(-1). The sigma2,3,7,8-PCDD/F dry deposition fluxes in the Marmara and Black Seas (210 kg year(-1)) are from 2 to 55 times higher than dry fluxes in the Mediterranean Sea (4-156 kg year(-1)). Analysis of estimated diffusive air-water fluxes and air/water fugacity ratios show that a net volatilization of some PCDD congeners is feasible. However, evidence of a net absorption flux for the rest of PCDD/F is found. When both atmospheric deposition processes are considered together the open Mediterranean Sea is a net sink of PCDD/F, due to the importance of dry deposition fluxes of aerosol-bound PCDDFs.

Polychlorinated biphenyls (PCBs) in the atmosphere of sub-alpine northern Italy.

The main objective of this work was to assess the atmospheric concentrations and seasonal variations of selected POPs in a sub-alpine location where few data are available. A monitoring and research station was set up at the JRC Ispra EMEP site (Italy). We present and discuss a one-year data set (2005-2006) on PCB air concentrations. Sigma 7PCBs monthly averaged concentration varied from 31 to 76 pgm(-3). Concentrations in the gas phase (21-72 pgm(-3)) were higher than those in the particulate phase (3-10 pgm(-3)). Advection of air masses and re-volatilization from local sources seem to play a dominant role as drivers of PCB atmospheric concentrations in the area. Indications of seasonal variation affecting PCB congener patterns and the gas/particulate partitioning were found. Modeling calculations suggest a predominant importance of the wet deposition in this region (1 microgm(-2)yr(-1) Sigma 7PCBs yearly total wet deposition flux; 650-2400 pgL(-1) rainwater concentrations).

Atmospheric input of POPs into Lake Maggiore (Northern Italy): PCDD/F and dioxin-like PCB profiles and fluxes in the atmosphere and aquatic system.

The delivery and accumulation of PCDD/Fs and dioxin-like PCBs (DL-PCBs) as recorded in sediments from the Lake Maggiore (LM) in Northern Italy and the influence of the atmosphere in contaminating this subalpine ecosystem were studied. PCDD/Fs (17 congeners) and DL-PCBs (12 congeners) concentrations, congener profiles and fluxes in air, bulk deposition, aquatic settling material and surface sediments are presented. Our strategy was to obtain surface sediment from areas near riverine inputs and in the depositional basins, settling material in sediment traps at one site and air, aerosol and bulk deposition profiles. PCDD/F concentrations in air of 25 WHO-TEQ fg m(-3) and DL-PCBs of 7 WHO-TEQ fg m(-3) were measured. Bulk atmospheric deposition yielded 140 and 28 WHO-TEQ pg m(-2) per week for dioxins/furans and DL-PCBs, respectively. Aquatic settling material exhibited concentrations of 11 WHO-TEQ pg g(-1) for PCDD/Fs and 2 WHO-TEQ pg g(-1) for DL-PCBs. Weekly settling material fluxes of 50 WHO-TEQ pg m(-2) and 10 WHO-TEQ pg m(-2) were obtained for PCDD/Fs and DL-PCBs, respectively. PCDD/Fs concentrations in surface sediments varied from 0.1 to 17 WHO-TEQ pg g(-1) whereas values ranged from 0.03 to 6 WHO-TEQ pg g(-1) for DL-PCBs. The concentrations obtained in the environmental compartments studied suggest a situation of low level contamination. PCDD/Fs and DL-PCBs congener profiles in atmospheric air, bulk deposition, aquatic settling matter and surface sediment point to an important if not dominant contribution from atmospheric deposition to Lake Maggiore, especially derived from wet deposition of aerosol-bound PCDD/Fs and DL-PCBs. Flux estimates support this hypothesis.

Atmospheric input of POPs into Lake Maggiore (Northern Italy): PBDE concentrations and profile in air, precipitation, settling material and sediments.

Large lakes are sinks for many chemical pollutants but the role of the atmosphere in delivering PBDEs (polybrominated diphenyl ethers) is not well known. In this study we estimated inputs of PBDEs from the atmosphere to Lake Maggiore and the delivery via settling material to accumulated bottom sediments. Sampling consisted of one simultaneous week of air and bulk deposition during Spring 2005, an integrated 4-month period of collected settling material (via sediment trap), and superficial bottom sediments near the sediment trap deployment and tributary mouths of the lake. Concentration of total PBDEs (Sigma 8) in the sediments ranged between 0.06 and 27 ng g(-1), and two different patterns were observed. One pattern was dominated by BDE-47 and BDE-99 and a second by BDE-209. The latter pattern suggested input from local source(s). Total PBDEs in air were 107 pg m(-3) with a pattern dominated by BDE-47. The bulk deposition rate of total PBDEs for precipitation was measurated to be 17.6 ng m(-2) day(-1) where BDE-209 exhibited the highest concentration. For aquatic settling material the flux was 3.57 ng m(-2) day(-1) and was dominated by congeners BDE-47 and BDE-99. The bulk deposition and settling material fluxes were in the same range for the less brominated congeners, while for the hepta- and deca-brominated PBDEs the fluxes in the settling material were one order of magnitude lower. This suggests different sedimentation processes among congeners and/or the presence of local sources that influence the relative distribution in water column.

Seasonal variations of selected herbicides and related metabolites in water, sediment, seaweed and clams in the Sacca di Goro coastal lagoon (Northern Adriatic).

This study assesses the status of Sacca di Goro coastal lagoon (Northern Adriatic, Italy) with respect to watershed pollution. Because 80% of its watershed is devoted to agriculture, plant protection products and their metabolites were found in the water column, sediments (the upper 0-15 cm layer), macroalgae (Ulva rigida) and clams (Tapes philippinarum). Five seasonal sampling campaigns were performed from May 2004 to April 2005 and concentrations measured in five stations in the lagoon and six in the watershed. Relatively high concentrations of the s-triazine - terbuthylazine -, urea herbicides - diuron - and alachlor were detected through the year mainly at stations directly influenced by the Po di Volano inflow. The concentrations of products in use follow a clear seasonal pattern with spring peaks. This pattern is also visible in the sediments as well as in biota. Among metabolites, hydroxylated compounds prevailed, often with concentrations greater than those of the parent compounds. For the most part of the year, the concentrations in biota were close to detection limits, with concentration peaks in spring.

Persistent organic pollutants in the dusts that settled across lower Manhattan after September 11, 2001.

The explosion and collapse of the World Trade Center (WTC) was a catastrophic event that produced an aerosol impacting many workers, residents, and commuters during the first few days after September 11, 2001. During the initial days that followed, 14 bulk samples of the settled dust were collected at locations surrounding the epicenter of the disaster, including one indoor location. Some samples were analyzed for many potential hazards, including inorganic and organic constituents as well as morphology. The results of the analyses for persistent organic pollutants are described herein, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and select organochlorine pesticides on settled dust samples. The sigma86-PCBs comprising less than 0.001% by mass of the bulk in the three bulk samples analyzed indicated that PCBs were of limited significance in the total settled dust across lower Manhattan. Likewise, organochlorine pesticides, including chlordanes, hexachlorobenzene, heptachlor, 4,4'-DDE, 2,4'-DDT, 4,4'-DDT, and Mirex, were found at low concentrations in the bulk samples. Conversely, the sigma37-PAHs comprised up to nearly 0.04% (<0.005-0.039%) by mass of the bulk settled dust in the six bulk samples. Further size segregation of these three initial bulk samples and seven additional samples indicates that sigma37-PAHs were found in higher concentrations on relatively large particles (10-53 microm), representing up to 0.04% of the total dust mass. Significant concentrations were also found on fine particles (<2.5 microm), often accounting for approximately 0.005% by mass. We estimate that approximately 100-1000 tons of sigma37-PAHs were spread over a localized area immediately after the WTC disaster on September 11.

Dynamic air-water exchange of polychlorinated biphenyls in the New York-New Jersey Harbor Estuary.

Simultaneous measurements of polychlorinated biphenyls (PCBs) in the air and water over Raritan Bay and New York Harbor were taken in July 1998, allowing the first determinations of air-water exchange fluxes for this heavily impacted system. Average gas-phase concentrations of sigmaPCBs were 1.0 ng m(-3) above Raritan Bay and 3.1 ng m(-3) above New York Harbor. A similar gradient was observed for dissolved water concentrations (1.6 and 3.8 ng L(-1), respectively). Shallow slopes of log K(oc) vs log K(ow) plots indicated a colloidal contribution to the dissolved concentrations, and a three-phase partitioning model was therefore applied. PCBs associated with colloids ranged from 6% to 93% for trichloro- to nonachlorobiphenyls, respectively. Air-water gas exchange fluxes of sigmaPCBs exhibited net volatilization for both Raritan Bay at +400 ng m(-2) day(-1) and New York Harbor at +2100 ng m(-2) day(-1). The correction for the colloidal interactions decreased the volatilization flux of sigmaPCBs by about 15%. Net air-water exchange fluxes of PCBs are expected to remain positive throughout the year due to the large water-air fugacity gradient and relatively constant seasonal water concentrations. The volatilization fluxes are approximately 40 times greater than atmospheric deposition of PCBs via both wet and dry particle deposition, suggesting that the estuary acts as a net source of PCBs to the atmosphere year-round.