Phosphorus fractionation in volcanic lake sediments (Azores - Portugal)

The phosphorus distribution in volcanic sediments of three lakes that are under different anthropogenic pressures in S?o Miguel island (Azores - Portugal) was evaluated using a sequential extraction scheme. The P-fractionation scheme employs sequential extractions of sediment with NH4Cl, bicarbonate-dithionite (BD), NaOH (at room temperature), HCl and NaOH (at 85 degrees C) to obtain five P-fractions. The P-fractionation shows that in lakes with higher trophic status (Lake Furnas and Lake Sete Cidades), the NaOH extracted P is the dominant fraction, that contribute with more than 50% to total sedimentary phosphorus. The rank order of P-fractionation for these two lakes was NaOH>NaOH (85 degrees C)>HCl>BD>NH4Cl for Furnas lake and NaOH>HCl>NaOH (85 degrees C)>NH4Cl>BD for Sete Cidades lake. On the other hand, the trend of P contribution in the oligotrophic lake Fogo shows that the most inert P pools have the higher concentrations, with more than 50% of the P contribution from the last extraction step with NaOH at 85 degrees C. For this lake, the rank order of P-fractionation was NH4Cl>BD>NaOH>HCl>NaOH (85 degrees C). The Phosphorus Maximum Solubilization Potential (P-MSP) was also calculated and the results show that for the more bio-available P-fractions (first and second extraction step), the P-MSP values for Furnas and Sete Cidades lakes are sensibly higher than the results obtained in Fogo lake, an indication of the non-point diffuse load discharged in the first ones.     

湖泊底泥磷释放及磷形态变化

为研究底泥中内源性磷释放对城市景观水体富营养化的影响,以西安市曲江南湖为对象,采用底泥磷形态标准测试方法(SMT)分析了磷的赋存形态,通过模拟实验探究了在不同环境条件(温度、pH和溶解氧)下磷形态变化的特征。结果表明:温度升高促进内源磷的释放,在夏季加剧水体富营养化程度;碱性条件有利于磷的释放,增大补给水源可减少底泥释磷量;厌氧环境下底泥释磷量是好氧时的3.96倍;Al-P 和Ca-P较稳定,在酸性条件下会加速其溶解;NH4+-P、 Fe-P 和OrgP受溶解氧、pH和温度影响较大,其吸附与释放能力有明显的差异。     

PCDD/Fs and PCBs in airborne particulate matter of the greater Thessaloniki area, N. Greece

Particle-bound polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were monitored at two sites in northern Greece for an eight-month period in 1999. PCDD/F concentrations were close to the lower end of reported values worldwide. Excepting a few cases, the PCDD/Fs homologue profile was stable. The gaseous PCDD/F fractions calculated were found to account for a small percentage of the total concentrations (<2% for OCDD/Fs and HpCDD/Fs, while 30-35% for TCDFs). Particle-bound PCBs were also found at low concentrations which, however, were higher at the urban site. Calculations of the dry deposition of particulate PCDD/ Fs and PCBs gave mean values of 0.52 and 0.59 pg I-TEQ/m2/day of PCDD/Fs, while 242 and 74 pg/m2/day of sigmaPCBs for the urban and the semirural areas respectively. An anticorrelation of PCDD/F concentrations with ambient temperature was derived particularly for the lower chlorinated congeners. A weak association with winds of western and southern origin was also observed. Factor analysis and literature source profiles were employed to identify possible emission sources. It was appeared that the PCDD/F compositional pattern of TSP is influenced by mixed sources the most prominent being uncontrolled fires and car exhausts.     

Temporal distribution and fractionation of polychlorinated biphenyl congeners in a contaminated Wisconsin lake

The most thorough field investigation, to date, of the temporal distribution and fractionation of polychlorinated biphenyl (PCB) congeners in an inland lake has been conducted in Little Lake Butte des Morts, WI. Distinct seasonal variations in dissolved and particle associated PCBs were observed over a two year period at the lake outlet; the lowest values occurred during ice-cover periods while the highest values occurred during summertime. Total dissolved PCBs ranged from 1.4–34 ng/L while total particle associated PCBs varied from 2.1–105 ng/L. An average of 71% of the total PCBs were associated with particles. Both PCB fractions were dominated by ortho-chlorinated di-, tri-, and tetrachlorobiphenyls with IUPAC #28+31 accounting for the greatest portion. Some changes appear to have taken place in the environmental composition of congeners since PCBs first entered this waterway through effluent discharges.     

N:P ratios,light limitation,and cyanobacterial dominance in a subtropical lake impacted by non-point source nutrient pollution

A long-term (28-year) data set was used to investigate historical changes in concentrations of phosphorus (P), nitrogen (N), N:P ratios, and Secchi disk transparency in a shallow subtropical lake (Lake Okeechobee, Florida, USA). The aim was to evaluate changes in the risk of N2-fixing cyanobacterial blooms, which have infrequently occurred in the lake's pelagic zone. Predictions regarding bloom risk were based on previously published N:P ratio models. Temporal trends in the biomass of cyanobacteria were evaluated using phytoplankton data collected in 1974, 1989-1992, and 1997-2000. Concentrations of pelagic total P increased from near 50 microg l-1 in the mid-1970s to over 100 microg l-1 in the late 1990s. Coincidentally, the total N:P (mass) ratio decreased from 30:1 to below 15:1, and soluble N:P ratio decreased from 15:1 to near 6:1, in the lake water. Published empirical models predict that current conditions favor cyanobacteria. The observations confirm this prediction: cyanobacteria presently account for 50-80% of total phytoplankton biovolume. The historical decrease in TN:TP ratio in the lake can be attributed to a decreased TN:TP ratio in the inflow water and to a decline in the lake's assimilation of P, relative to N. Coincident with these declines in total and soluble N:P ratios, Secchi disk transparency declined from 0.6 m to near 0.3 m, possibly due to increased mineral turbidity in the lake water. Empirical models predict that under the turbid, low irradiance conditions that prevail in this lake, non-heterocystous cyanobacteria should dominate the phytoplankton. Our observations confirmed this prediction: non-N2-fixing taxa (primarily Oscillatoria and Lyngbya spp.) typically dominated the cyanobacteria community during the last decade. The only exception was a year with very low water levels, when heterocystous N2-fixing Anabaena became dominant. In the near-shore regions of this shallow lake, low N:P ratios potentially favor blooms of N2-fixing cyanobacteria, but their occurrence in the pelagic zone is restricted by low irradiance and lack of stable stratification.     

Accumulation and fractionation of copper, iron, manganese, and zinc in calcareous soils amended with composts.

Amending soils with compost may lead to accumulation of metals and their fractions at various concentrations in the soil profile. The objectives of this study were to determine 1) the accumulation of Cu, Fe, Mn, and Zn with depth and 2) the distribution of water soluble, exchangeable, carbonate, Fe-Mn oxides, organic and residual forms of each metal in soils amended with MSW compost, co-compost, biosolids compost and inorganic fertilizer (as control). Total concentrations of Cu, Fe, Mn and Zn were concentrated in the 0-22 cm soil layer and scant in the rock layer. These metals were in the decreasing order of Fe > Mn > Zn > or = Cu. Copper, Fe, and Zn were predominantly in the residual form followed by fractions associated with Fe-Mn oxides, carbonate, organic, exchangeable and water soluble in all treatments except MSW compost amended soil where the organic fraction was higher than the carbonate fraction. In fertilizer, co-compost and biosolids compost treated soils Mn concentrated mainly in the Fe-Mn oxides form followed by residual, carbonate, and organic forms whereas, in MSW compost treated soil the same pattern occurred except that Mn organic fraction was higher than that in the carbonate form. The MSW compost has a greater potential to be used as a soil amendment to supply plants with Cu, Mn and Zn than other treatments in calcareous soils of south Florida.     

Organic chlorine compounds in lake sediments. IV. Dioxins, furans and related chloroaromatic compounds

Polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), polychloronaphthalenes (PCNs) and coplanar PCBs were measured in surface sediments from 18 lake areas in Central Finland. Toxic 2, 3, 7, 8-substituted PCDD and PCDF congeners occurred at low levels (<20 − 230 pg/g dw). PCNs appeared at few ng/g (total PCNs) levels. Pulp mills or any other local sources could not be associated with the sedimented PCDDs, PCDFs and PCNs. Coplanar PCB congeners 77 and 105 (IUPAC Nr) were generally found at 20–550 pg/g levels. The most toxic congener 126 was measured (110 pg/g) only at one area near a local PCB leakage. Pulp mill originated aromatic chlorocompounds which coelute with PCDDs and PCDFs in clean up, probably alkyl polychlorobibenzyls (R-PCBBs) appeared at ng/g levels and showed a clear gradient dowstreams from pulp mill effluent points.     

Sea-breeze circulation and photochemical pollution in Athens,Greece

The purpose of this paper is to analyse the effect of the sea-breeze on photochemical pollution in Athens, Greece. To this end, the SO₂, NO, NO₂, O₃ and CO concentrations, the vertical structure of the atmospheric boundary layer, the pollution emission rates and wind data are examined simultaneously for two typical days in August 1981 with well-defined sea-breeze circulation. The tendency of the complicated seabreeze flow field to stratify the atmosphere and thus generate layers with different constituents affects the concentrations measured near the ground and causes relatively high oxidant levels at night. As inversion layers descend or disappear, abrupt changes and short-period oscillations in concentrations are found, and can be explained by a simple multilayer box model. The diurnal variation and considerations based on simple ground-level wind trajectories indicate that recirculation of pollutants by the sea-breeze cell takes place, possibly aided by the small size of the basin and the closed topography. The passage of the sea-breeze front seems to have no direct effect. No day-to-day pollution accumulation is noticed. Thus, it becomes clear that if modeling of photochemical pollution in such coastal regions with pronounced relief is to be successful, it needs to pay close attention to both the flow field details and the vertical structure of the atmosphere, especially the ground-based inversion break-up and boundary layer collapse.     

Organic chlorine compounds in lake sediments. III. Chlorohydrocarbons, free and chemically bound chlorophenols

Chlorohydrocarbons and free and chemically bound chlorophenols, catechols and guaiacols were measured from lake sediments in Central Finland. Chlorohydrocarbons occurred at low backround levels except chlorocymenes from pulp mills and PCBs near the city of Äänekoski, where a local leakage occurrs. Free chlorophenols (hexane extractables) were found in all 18 areas studied, but the bound ones (extracted with strong alkali) only in the pulp mill reciepient lakes where they dominated. Preliminary analyses of chemically bound chlorophenols in high molecular fractions of spent bleach liquors and pulp mill effluents indicated that majority of chlorocatechols and guaiacols are bound already in the factory.     

Cesium-137 and mercury contamination in lake sediments.

The contribution of fluvial discharge and global fallout of 137Cs and mercury to sedimentation fluxes in Lake Shinji and Lake Nakaumi, Japan, was studied. The fluvial flux through soil erosion accounted for 11 to 27% of accumulated 137Cs in the sediments in the 1950's and 1960's, which were the periods of the most extensive atmospheric input, and for 90 to 100% in the 1990's. The vertical profiles of mercury concentrations in the lake sediments studied showed a maximum between 1959 and 1963, which was originated mostly from the extensive use of mercury-agrochemicals in paddyfields of the watershed in the past. These findings are representative examples of long-term contamination of lake sediments caused by the contaminated ground soil erosion.     

Particulate and sulfur dioxide concentration measurements in Patras,Greece

The purpose of this study was to obtain a better assessment of the Patras, Greece, air quality, in terms of the primary pollutants total suspended particulates (TSPs) and sulfur dioxide (SO2), because limited and short-duration measurements have been conducted in the past. Installation and operation of a mobile air monitoring station at two different locations in the Patras downtown area and one location in the outskirts of the city was undertaken and covered the periods July 1, 1994-January 30, 1995; March 18-August 23, 1995; and April 19-July 27, 1996, respectively. For both pollutants measured at each location, the monthly average concentrations and typical weekly variation of daily averages, as well as the diurnal variations and frequency concentration distributions in each month of the monitoring periods, were calculated and are presented in bar diagrams. The annual and winter period medians and the annual 98th percentile were also calculated and are compared with the limit and guide values provided by the European Economic Community Council Directive 80/779/EEC. In addition, comparison of SO2 values is made with the limit values adopted by the more recent Directive 1999/30/EC. It was found that the TSP and SO2 levels at all locations were very low and were lower than the levels found in Thessaloniki and Athens, Greece. An attempt to explain what had been measured is also undertaken. The data presented are considered essential for future reference and comparison purposes.     

Photochemical formation and transport of ozone in Athens,Greece

An evaluation of the diurnal variation of the hourly ozone concentrations measured at five sites in Greater Athens from June until early September 1984 indicates that photosmog episodes in Greater Athens are associated with the sea breeze circulation. Due to local air circulation in the Athens basin, precursors of O₃ are transported to and accumulated in the Saronikos Bay during the morning hours while the land breeze is blowing. At noon, when the sea breeze sets in, the O₃ formed over the sea is brought back to the coast and to central Athens where it increases the local O₃ concentration by a factor of 3–5 within a few hours. The O₃ levels often remain high throughout the night. During the photochemical smog episodes, all of them accompanied by well-developed sea breezes, the U.S. Air Quality Standard of 120 ppb O₃ was exceeded for 4–7 h day⁻¹. Peak O₃ concentrations up to nearly 200 ppb were recorded in the smog episodes.Relatively high O₃ concentrations were measured on the island of Aegina. They tend to remain high during the night and can be attributed only to primary pollutant transport from Greater Athens advected by the land breeze. The O₃ values obtained at Mount Immitos (1000 m above MSL) suggest that, first, the sea breeze inhibits the influence of vertical thermal convection up to heights above 600 m, and second, no O₃ is noticeable from above the tropopause to ground level or from long-range transport.     

Particulate and Sulfur Dioxide Concentration Measurements in Patras,Greece

Abstract

The purpose of this study was to obtain a better assessment of the Patras, Greece, air quality, in terms of the primary pollutants total suspended particulates (TSPs) and sulfur dioxide (SO₂), because limited and short-duration measurements have been conducted in the past. Installation and operation of a mobile air monitoring station at two different locations in the Patras downtown area and one location in the outskirts of the city was undertaken and covered the periods July 1, 1994-January 30, 1995; March 18-August 23, 1995; and April 19-July 27, 1996, respectively. For both pollutants measured at each location, the monthly average concentrations and typical weekly variation of daily averages, as well as the diurnal variations and frequency concentration distributions in each month of the monitoring periods, were calculated and are presented in bar diagrams. The annual and winter period medians and the annual 98th percentile were also calculated and are compared with the limit and guide values provided by the European Economic Community Council Directive 80/779/EEC. In addition, comparison of SO₂ values is made with the limit values adopted by the more recent Directive 1999/30/EC. It was found that the TSP and SO₂ levels at all locations were very low and were lower than the levels found in Thessaloniki and Athens, Greece. An attempt to explain what had been measured is also undertaken. The data presented are considered essential for future reference and comparison purposes.     

Chemical fractionation of copper, lead and zinc in ombrotrophic peat

Measurement of operationally defined chemical fractions in ombrotrophic peat samples provides information not obtained by total metal extractions. Examination of such sequential data permits interpretation of process dynamics. Results for copper, lead and zinc chemical fractionation of peat profiles from Ringinglow Bog, near Sheffield, Great Britain, are reported and discussed. Lead and zinc share similar patterns of partitioning. A considerable proportion of these records is in a form predisposed to transformation and mobilisation. In contrast, much of the copper is comparatively immobile, it being associated with the more chemically intractable fractions. The results suggest that peat copper deposition records may be used for reconstruction of pollution history. The use of lead and zinc records for these purposes is problematic.     

Phosphorus release in aerobic sludge digestion.

The objectives of this study are to examine the phosphorus release in aerobic sludge digestion and to better understand its governing mechanisms. In this study, phosphorus release was examined using the secondary sludge from both conventional and biological nutrient removal processes. The experiments were carried out at room temperature (22 +/- 2 degrees C), with or without automatic control of pH (4.5 to 7.8), and under three aeration schemes: fully aerobic (dissolved oxygen [DO] at 3 to 4 mg/L), low DO (0.2 to 0.8 mg/L), and cyclic (with alternate on/off aeration). The released phosphorus concentrations were 20 to 80 mg/L for the conventional sludge and 60 to 130 mg/L for the biophosphorus sludge. Higher phosphorus release also occurred at low pH (<6.0). As for the effect of DO, fully aerobic digestion caused higher phosphorus release than the low-DO and cyclic operations. For better understanding, the solid phosphorus in sludge was conceptually categorized into three forms: inorganic phosphorus precipitates, organic cellular phosphorus, and polyphosphate (poly-P) in polyphosphate-accumulating organisms. Dissolution of inorganic phosphorus precipitates is controlled by physical and chemical conditions, with pH being the most important in this study. Lowering the pH to 4 to 6 clearly promoted the release of inorganic phosphorus. Polyphosphate hydrolysis, on the other hand, was found to be regulated biologically (sensitive to occurrence of anaerobic conditions) and was insignificant in the glutaraldehyde-fixed sludge. Phosphorus release from organic phosphorus should correlate with the volatile solid (VS) digestion, which lyses the cells and frees the phosphorus covalently bonded with the organic matters. The amounts of phosphorus released per unit VS digested (deltaP/deltaVS) were therefore calculated for experiments with long periods of constant pH (to minimize interferences from dissolution/precipitation of inorganic phosphorus). The results suggested that some poly-P was hydrolyzed and released accompanying the aerobic VS digestion, but at rates far lower than those under anaerobic conditions.     

Long-term variation in surface ozone and its precursors in Athens,Greece

INTENTION, GOAL, SCOPE, BACKGROUND: Photochemical pollution is a very complex process involving meteorological, topographic, emission and chemical parameters. The most important chemical mechanisms involved in the atmospheric process have already been identified and studied. However, many unknown parameters still exist because of the large number of participating chemical reactions. OBJECTIVE: The present study investigates the processes involved in the photochemical pollution effect of an urban station located in the greater area of the Athens basin and gives a plausible explanation for the different seasonal ozone development between that station and another rural one. Furthermore, the distribution of the mean monthly surface ozone observed at the urban station during 1987-2001 is examined in order to create a relevant forecasting tool. METHODS: Averaged hourly data of O3 and NOx observations monitored at the above mentioned stations, during 1987-2001, have been used in order to derive the daytime (7:00-15:00) values. Trajectories calculated by using a 2D-trajectory code and meteorological data, during the period 1988-1996, have also been used. RESULTS AND DISCUSSION: At the urban station, the percentage negative trend of NO and NOx data in winter and summer is higher than that in spring and autumn, while the percentage ozone trend is maximum in the summer. On the contrary, the negative surface ozone trend at the rural station exhibits a minimum in summer and a maximum in autumn and winter. The mean seasonal wind-rose for the selected months shows that the northward wind flow dominates during June, the month of the lowest negative ozone trend in the rural station. Finally, the development of the forecasting tool shows that the mean monthly surface ozone data during the period (1987-2001) demonstrates a semi-log distribution. CONCLUSIONS: Air transport effect on the air pollution of the rural station (not blocked by mountains) is deduced as a possible reason for the different seasonal ozone development observed between the rural and the urban station. Finally, the discrepancies between the theoretical probabilities deduced by the model and the empirical ones appear to be very small, and the corresponding correlation coefficient is 0.99. RECOMMENDATION AND OUTLOOK: However, to interpret the aforementioned statistical results about the negative trends in ozone and its precursors, additional parameters can be taken into account. Changes in NOx concentrations, for instance, can result not only from changes in emissions or meteorological conditions. There might also be a contribution through changes in the atmospheric composition. A study of the contribution of changes in atmospheric composition to trends of observed NOx concentrations requires that a series of steps be taken (removal of meteorological influence in the time series, calculation of trends in OH concentrations, etc.).     

Volatile hydrocarbons in the atmosphere of Athens,Greece

This work presents the results of one-year monitoring study of Volatile Hydrocarbons, VHCs, in the atmosphere of Athens. It is the first systematic attempt to determine the VHC levels in the Athens' atmosphere with the very well known photochemical pollution problems. The purpose of this work was to create a database concerning VHCs in order to evaluate the photochemical pollution in this area (ozone creation, case studies and meteorology). Totally, 308 samples were collected at three different sites used in the state-monitoring programme involving the criteria pollutants. Air samples were collected on Tenax TA tubes and analysed by thermal desorption and dual column GC dual FID. Fifteen selected compounds were studied; 6 alkanes and 9 benzenoid compounds. The measured values of individual alkanes ranged from 0.39 pg m(-3) to 33 pg m(-3), and those of aromatics from 0.20 pg m(-3) to 616 pg m(-3). The sum of all 15 VHC concentrations ranged between 16 and 1697 pg m(-3). The time and spatial variations in the concentration of these compounds were assessed. Volatile hydrocarbons exhibited a clear seasonal and time cycle, showing higher concentrations during winter and early morning hours. Study of the spatial variations of VHC levels showed higher concentrations at the center of the city. The variation of toluene/benzene ratio and the correlation between VHCs, criteria pollutants (CO, NOx and O3) and meteorological parameters were also assessed. It was demonstrated that a trip-line of the VHCs concentration at the city center doubles the ozone concentration at peripheral areas under favourable meteorological conditions.     

PM10 regional transport pathways in Thessaloniki,Greece

In this study, the most dominant regional transport pathways for the city of Thessaloniki, Greece were identified and linked to air quality issues with respect to particulate matter (PM). Using air mass trajectories, cluster analysis techniques and PM10 measurements of a background-urban station of the greater Thessaloniki area during 2001–2004, it was found that north-eastern and southern flows were the most frequent in appearance with high potential to influence the city of Thessaloniki, especially when coinciding with biomass burning or Saharan dust events correspondingly. These incidents appeared to occur mostly during summer adding to a PM10 monthly mean up to 10 μg m^?3. High concentrations of surface PM10 related to north-eastern flows were in most cases accompanied with high aerosol columnar optical depths implying that particulate matter transport from the North-East was multi-layered. South-southwesterly flows originating from N. Africa, though less frequent, seemed to affect decisively Thessaloniki's aerosol budget especially during transition seasons. These flows were related with an increase of the monthly PM10 average up to 20–30 μg m^?3 for the time period studied. Finally, northerly flows were found to transport rather clean air masses that did not seem to contribute to the air quality deterioration of the city.     

Determination of PAN,PPN, PnBN and selected pentyl nitrates in Athens,Greece

Quasi-continuous measurements of PAN, PPN, PnBN and the alkyl nitrates—2-methyl-2-butyl nitrate, 3-pentyl nitrate and 2-pentyl nitrate were carried out in Athens using a simple cryoconcentration technique. The maximum mixing ratios measured were 6.6, 1.0 and 0.07 ppbv for PAN, PPN and PnBN, respectively, for the peroxyacyl nitrates, and 0.3, 0.09 and 0.03 ppb for 2-methyl-2-butyl nitrate, 2-pentyl nitrate and 3-pentyl nitrate, respectively. Mean ratios of PPN/PAN mixing ratios were 0.102 and of PnBN/PAN 0.012. 2PN/3PN mean ratios were 1.8 near the theoretical value of 1.6. All maximum values of measured nitrogenous compounds were associated with maximum mixing ratios of ozone and NO_x and occurred when southwestern winds prevailed in association with a temperature inversion.