Butyltin levels in several Portuguese coastal areas

This work aimed to report present levels (2007–2008 sampling) of tri- (TBT), di- (DBT), and monobutyltin (MBT) in surface sediments from 11 Portuguese coastal sites and discuss the evolution of BTs contamination in the last two decades. All the samples revealed quantifiable values of TBT, DBT, and MBT with total butyltin concentrations between 1 and 565 ng/g (of Sn in dry sediment). Maximum level of TBT, 66 ng/g, was observed in Sado estuary, at Lisnave site, in the proximity of a big shipyard. MBT decreased site by site by the same order as DBT and TBT did, but its concentrations were much higher in many cases, denoting that TBT contamination was much higher in the past. A comparison with the available previous data confirmed a marked decrease of TBT contamination all over the last years, indicating that the main sources of TBT in Portuguese coastwise stopped effectively.     

Determination of the insecticide diflubenzuron in mushrooms by kinetic method and high-performance liquid chromatographic method

In the present study, a new sensitive and simple kinetic-spectrophotometric method for the determination of the insecticide diflubenzuron [1-(4-chlorophenyl)-3-(2,6-diflubenzoil)urea] is proposed. The method is based on the inhibited effect of diflubenzuron on the oxidation of sulphanilic acid (SA) by hydrogen peroxide in phosphate buffer in presence Cu(II) ion. Diflubenzuron was determined with linear calibration graph in the interval from 0.31 to 3.1 μg mL?1 and from 3.1 to 31.0 μg mL?1. The optimized conditions yielded a theoretical detection limit of 0.18 μg mL?1 corresponding to 0.036 mg kg(-1)mushroom sample based on the 3S(b) criterion. The RSD is 5.03-1.83 % and 2.81-0.71 % for the concentration interval of diflubenzuron 0.31-3.1 μg mL?1 and 3.1-31.0 μg mL?1, respectively. The reaction was followed spectrophotometrically at 370 nm. The kinetic parameters of the reaction are reported, and the rate equations are suggested. The developed procedure was successfully applied to the rapid determination of diflubenzuron in spiked mushroom samples of different mushroom species. The HPLC method was used like a comparative method to verify results.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Storage and distribution of trace metals and spheroidal carbonaceous particles (SCPs) from atmospheric deposition in the catchment peats of Lochnagar, Scotland.

Lochnagar is a remote mountain lake to the south-east of the Cairngorm region in Scotland. Its catchment receives anthropogenic trace metals solely from atmospheric deposition. Ten peat cores were taken from the catchment and analysis confirmed that they have been contaminated by trace metals. The peats have an high affinity for trace metals and this results in metal accumulation in the surface peat layers. The formation of trace metal sulphides may also reduce remobilisation. In this way, trace metals derived from atmospheric deposition have been scavenged and accumulated. In contaminated peat layers, 77.4% Hg, 89.6% Pb, 93.4% Cu, 72.4% Zn and 86.5% Cd of the total stored are from anthropogenic sources. The accumulated trace metals in the peats can potentially influence the lake system through erosion. Spheroidal carbonaceous particle (SCP) profiles were used to date the peat cores. By referring to the SCP profiles in the peats and comparing these with the trace metal profiles in the lake sediments, the mobility of trace metals in the catchment peats is confirmed.     

Modeling the exposure of children and adults via diet to chemicals in the environment with crop-specific models

Exposure to chemicals via diet is a major uptake pathway for many compounds but is often estimated in a rather generic way. We use a new model framework (NMF) with crop-specific models to predict the dietary intake by 4-5-year-old children and 14-75-year-old women of three environmental compounds from their background concentrations in soil and air. Calculated daily intakes of benzo(a)pyrene and 2,3,7,8-TCDD are in good agreement with measured results from diet studies. The major source of both compounds in human diet is deposition from air. Inhalation of air and ingestion of soil play a minor role. Children take up more than twice the amount than adults per kg bodyweight, due to higher consumption per kg bodyweight. Contrary, the methods for indirect human exposure suggested in the Technical Guidance Document (TGD) for chemical risk assessment in the EU lead to overprediction, due to unrealistic consumption data and a false root model.     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 2-Polychlorinated biphenyls

The temporal variability and bioaccumulation dynamics of individual PCBs were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the polluted Buenos Aires coastal area. Fish muscles contain high concentrations of total PCBs (11+/-7.2, 4.6+/-3.4 or 19+/-13 microg g(-1), dry, fresh and lipid weight, respectively) reflecting chronic bioaccumulation from sewage-industrial particulates. On a temporal basis, lipid normalized PCBs concentrations peaked by the end of 2001-2002 coincident with the rainiest period over the last four decades and shortly after PCB prohibition in the country, reflecting massive discharges to the coastal ecosystem. PCB composition in fish muscles show a prevailing contribution of hexachlorobiphenyls (35+/-4.2%), followed by hepta (23+/-3.0%), penta (20+/-3.6%), tri-tetra (16+/-4.8%) and minor proportions of octa-decachlorobiphenyls (5.7+/-3.1%) similar to an Aroclor 1242-1254-1260 1:2:4 mixture. During 2001-2002 maxima fish showed an enrichment in tri-tetrachlorobiphenyls ( approximately 1242-1254-1260 1:1:1 mixture) denoting a fresher signature. Fish/settling material lipid-organic carbon accumulation factors (BSAFs: 2.4-46, average: 21+/-10) plotted against kow showed a parabolic trend (BSAFs=-0.38 log kow2 + 5.16 log kow -15.85; R2=0.46) maximizing at hexa, hepta and octachlorobiphenyl 203 with reduced bioaccumulation of a few hepta (170, 191) and most octa-decachlorobihenyls suggesting limited intestinal absorption.     

Effect of coumaphos on cholinesterase activity, hematology, and biochemical blood parameters of bovines in tropical regions of Mexico

To assess the effect of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] exposure on physiological responses during bovine production, acetylcolinesterase (AChE) and butyrylcholinesterase (BuChE) activities were measured in whole blood, erythrocytes, and plasma of healthy male steers (Bos Taurus x Bos indicus) sprayed with coumaphos at a non-lethal dose of 1 mg kg(- 1) body weight per day once every 14 (in vivo group) or 21 days (southern and central groups). Coumaphos topically administered at 1 mg/kg body weight per day to cattle under normal management practices in tropical areas produced a significant inhibition in erythrocyte (RBC) AChE and BuAChE activities when compared to baseline levels. RBC-AChE activity for the in vivo group decreased 71.3% (P < 0.05) and BuChE activity 59.1% (P < 0.05); RBC-AChE activity decreased 55.1% (P < 0.05) (southern group) and 43.4% (P < 0.05) (central group). Compared to the control specimens, steers from in vivo, southern, and central groups after 150 days of exposure had lower (P < 0.05) leukocyte count, absolute lymphocyte, erythrocyte, and platelet counts. Decreases in RBC-AChE activities correlated with decreased lymphocyte (r = 1.000, p = 0.01), erythrocyte (r = 1.000, p = 0.003), and platelet counts (r = 0.841, p = 0.036). Significantly increased BUN levels (P < 0.05) correlated with the decrease in RBC-AChE activities (r = - 0.997, p = 0.047) and with the decrease in absolute red blood cell (r = - 0.883, p = 0.020) and lymphocyte (r = - 0.825, p = 0.043) counts; increased (P < 0.05) total plasma protein levels correlated with the decrease in RBC-AChE activities (r = -0.998, p = 0.043), absolute red blood cell (r = - 0.998, p = 0.040), lymphocyte (r = - 0.893, p = 0.017), and platelet (r = -0.855, p = 0.030) counts. The physiological responses correlated with the erythrocyte acetylcholinesterase inhibition could be considered as early indicators or warning responses of bovine exposures to organophosphorus pesticides (OPs).     

Treatment of drainage water with industrial by-products to prevent phosphorus loss from tile-drained land

Tile drained land with phosphorus (P)-rich topsoil is prone to P loss, which can impair surface water quality via eutrophication. We used by-products from steel and energy industries to mitigate P loss from tile drains. For each by-product, P sorption maximum (P(max)) and strength (k) were determined, while a fluvarium trial assessed P uptake with flow rate. Although two ash materials (fly ash and bottom ash) had high P(max) and k values, heavy metal concentrations negated their use in the field. The fluvarium experiment determined that P uptake with by-products was best at low flow, but decreased at higher flow in proportion to k. A mixture of melter slag (<10 mm) and basic slag (high P(max), 7250 mg kg(-1); and k, 0.508 L mg P(-1)) was installed as backfill in eight drains on a dairy farm. Four drains with greywacke as backfill were constructed for controls. The site (10 ha) had P-rich topsoil (Olsen P of 64 mg kg(-1)) and yielded a mean dissolved reactive P (DRP) and total P (TP) concentration from greywacke backfilled drains of 0.33 and 1.20 mg L(-1), respectively. In contrast, slag backfilled drains had DRP and TP concentrations of 0.09 and 0.36 mg L(-1), respectively. Loads of DRP and TP in greywacke drains (0.45 and 1.92, respectively) were significantly greater (P < 0.05) than those from slag drains (0.18 and 0.85, respectively). Data from a farm where melter slag was used as a backfill suggested that slag would have a life expectancy of about 25 yr. Thus, backfilling tile drains with melter slag and a small proportion of basic slag is recommended as an effective means of decreasing P loss from high P soils.     

Recovery of zinc and lead from fly ash from ash-melting and gasification-melting processes of MSW--comparison and applicability of chemical leaching methods

Fly ash generated from MSW ash-melting and gasification-melting plants, known as Melting Furnace Fly Ash (MFA), contains considerable amounts of heavy metals such as Pb and Zn. These metals can be recovered using a smelting furnace after "pre-treatment" for removal of unnecessary elements such as Cl, Sn and Si. Chemical methods have been studied for pretreatment in the past. However, they have been discussed only with regard to treatment cost and the concentration of Pb and Zn recovered, but neither applicability to various types of MFA nor the environmental impact have been considered. In this study, acid, alkaline and ammonia/chloride leaching methods were compared from the standpoints of: (1) applicability to MFA, (2) concentration of Pb and Zn recovered, (3) treatment cost, and (4) environmental impact. Twenty-three samples of MFAs were collected and classified into 4 types based on element contents. A Pb and Zn recovery experiment was conducted for the representative MFA of those types. The results showed: (1) MFA from gasification-melting plants cannot be treated by chemical methods; (2) the other MFA can be treated to an acceptable quality by existing smelting furnaces; (3) only MFA from electric resistance ash-melting plants can be treated easily by the water washing method; and (4) alkaline and ammonia/chloride leaching methods were more effective than acid leaching.