Potential dermal exposure to deltamethrin and risk assessment for manual sprayers: influence of crop type

A comparison of the Potential Dermal Exposure (PDE) of workers to the insecticide deltamethrin was made as a function of crop type, in small agricultural production units in Argentina. Seven experiments were done with two different crops (maize and broccoli, treated area between 600 and 1000 m(2)) with three different operators under typical field conditions using a lever operated knapsack. The methodology is based on the whole body dosimetry technique, presenting separately the data for mixing/loading and application activities. These results indicate a higher concentration of pesticide in lower body sections for broccoli and a wider distribution for maize. The risk inherent in these agricultural procedures is estimated through Margin of Safety (MOS) values and was found to be generally safe. Preliminary results of a mass balance distribution of the pesticide between crop, soil and operator are also presented.     

Effects of chelates on plants and soil microbial community: comparison of EDTA and EDDS for lead phytoextraction

Most studies on chelate-induced phytoextraction have focused on EDTA-mediated Pb phytoextraction. But EDTA and the formed EDTA-Pb complexes have low biodegradability and high solubility in soil, resulting in an elevated risk of adverse environmental effects. EDDS is an easily biodegradable chelating agent that has recently been proposed as an environmentally sound alternative to EDTA. Consequently, a greenhouse experiment, using a completely randomized factorial design with four replications, was carried out to compare the potential of EDTA and EDDS for chelate-induced Pb phytoextraction with Cynara cardunculus, as well as to investigate the toxicity of these two chelates to both cardoon plants and soil microorganisms. The effects of chelate addition on soil microbial communities were studied through the determination of a variety of biological indicators of soil quality such as soil enzyme activities, basal and substrate-induced respiration, potentially mineralizable nitrogen, and community level physiological profiles. EDTA was much more efficient than EDDS for the enhancement of root Pb uptake and root-to-shoot Pb translocation. In a soil polluted with 5000 mg Pb kg(-1), as a result of the addition of 1 g EDTA kg(-1) soil, a value of 1332 mg Pb kg(-1) DW shoot was obtained. EDDS application resulted in a shoot Pb accumulation of only 310 mg kg(-1)DW. Plants treated with EDDS showed lower values of biomass than those treated with EDTA. EDDS proved to be rapidly degraded, and less toxic to the soil microbial community in control non-polluted soils. Pb-polluted EDDS-treated soils showed significantly higher values of basal and substrate-induced respiration than those treated with EDTA. Although EDDS had a lower capacity to enhance Pb phytoextraction than EDTA, it has the advantage of rapid biodegradation.     

Fate of coagulant species and conformational effects during the aggregation of a model of a humic substance with Al13 polycations

A model of a humic substance (MHS) obtained from auto-oxidation of catechol and glycine, was aggregated at pH 6 and 8 with Al(13) polycations. The fate of Al(13) coagulant species upon association with MHS functional groups was studied using solid state (27)Al Magic-angle spinning (MAS) NMR and CP-MAS (13)C NMR. Electrophoretic measurements and steady-state fluorescence spectroscopy with pyrene as a fluoroprobe, were combined to investigate structural re-organization of humic material with aluminum concentration. MAS (27)Al NMR revealed that the coagulant species are Al(13) polycations or oligomers of Al(13) units at both pHs. CP MAS (13)C spectra indicated that, at low Al concentration, hydrolyzed aluminum species bind selectively to carboxylic groups at pH 6 and to phenolic moieties at pH 8. At higher coagulant concentrations, the remaining functional groups also interact with hydrolyzed Al to yield similar CP MAS (13)C spectra in the optimum concentration range. Negative values of electrophoretic mobility were obtained at optimum coagulant concentrations even though an overall charge balance was achieved between MHS anionic charge and Al(13) cationic charge at pH 6. The polarity-sensitive fluorescence of pyrene revealed that the interaction of Al(13) coagulant species with MHS functional groups induces the formation of intramolecular hydrophobic microenvironments. Such structural changes were reversed upon further addition of Al(13) polycations.     

Recovery and detection of Cryptosporidium parvum oocysts from water samples using continuous flow centrifugation

Continuous flow centrifugation (CFC) was used in conjunction with immunomagnetic separation (IMS) and immunofluorescence microscopy (IFA) and nested PCR to recover and detect oocysts of Cryptosporidium parvum and cysts of Giardia intestinalis from 10L volumes of source water samples. Using a spiking dose of 100 oocysts, nine of 10 runs were positive by IFA, with a mean recovery of 4.4+/-2.27 oocysts; when another 10 runs were analyzed using nested PCR to the TRAP C-1 and Cp41 genes, nine of 10 were positive with both PCR assays. When the spiking dose was reduced to 10 oocysts in 10L, 10 of 12 runs were positive by IFA, with a mean oocyst recovery of 3.25+/-3.25 oocysts. When 10 cysts of Giardia intestinalis were co-spiked with oocysts into 10L of source water, five of seven runs were positive, with a mean cyst recovery of x=0.85+/-0.7. When 10 oocysts (enumerated using a fluorescence activated cell sorter) were spiked into 10L volumes of tap water, one of 10 runs was positive, with one oocyst detected. For the majority of the source water samples, turbidities of the source water samples ranged from 1.1 to 22 NTU, but exceeded 100 NTU for some samples collected when sediment was disturbed. The turbidities of pellets recovered using CFC and resuspended in 10 mL of water were very high (exceeding 500 NTU for the source water-derived pellets and 100 NTU for the tap water-derived pellets). While not as efficient as existing capsule-filtration based methods (i.e., US EPA methods 1622/1623), CFC and IMS may provide a more rapid and economical alternative for isolation of C. parvum oocysts from highly turbid water samples containing small quantities of oocysts.     

Removal of persistent pharmaceutical micropollutants from sewage by addition of PAC in a sequential membrane bioreactor

The performance of a membrane bioreactor operating in a sequential mode (SMBR) using an external flat-plate membrane was investigated. After 200 days of operation, a single addition of 1 g L⁻¹ Powdered Activated Carbon (PAC) was added directly into the mixed liquor in order to enhance the simultaneous removal of nutrients and pharmaceutical micropollutants from synthetic urban wastewater. Throughout the entire operation (288 days), Chemical Oxygen Demand (COD) removal efficiencies were up to 95%, ammonium nitrogen removal was maintained over 70-80%, whereas phosphorus removal achieved only high values (around 80%) after PAC addition. During the operation of the SMBR without PAC addition, micropollutants which exerted a more recalcitrant behaviour were carbamazepine, diazepam, diclofenac and trimethoprim, with no significant removal. On the other hand, moderate removals (42-64%) were observed for naproxen and erythromycin, whereas ibuprofen, roxithromycin and fluoxetine were removed in the range of 71-97%. The addition of PAC into the aeration tank was a successful tool to improve the removal of the more recalcitrant compounds up to 85%. The highest removal with PAC was observed for carbamazepine, trimethoprim as well as for roxithromycin, erythromycin and fluoxetine. The latter four compounds have amine groups and pKa in the range 6.7-10.1, thus the interaction between PAC and the positively charged amino groups might be the cause of their comparatively better results. Microbial ecology present in the biomass showed a higher abundance of Accumulibacter phosphatis as well as the ammonium oxidizing bacteria belonging to the genus Nitrosomonas after PAC addition.     

The analysis of PM2.5 and associated elements and their indoor/outdoor pollution status in an urban area

In this study, elemental composition of PM2.5 and the status of indoor/outdoor pollution were investigated in a commercial building near a roadside area in Daejeon, Korea. A total of 60 parallel PM2.5 samples were collected both on the roof (outdoor) and in an indoor office of a building near a highly congested road during the spring and fall of 2008. The concentrations of 23 elements were analysed from these PM2.5 samples using instrumental neutron activation analysis. PM2.5 levels in indoor environment (47.6 ± 16.5 μg/m(3)) were noticeably higher than the outdoor levels (37.7 ± 17.2 μg/m(3)) with the I/O concentration ratio of 1.37 ± 0.33 [correlation coefficient (r) = 0.89, P < 0.001]. Principal component analysis results coincidently showed the predominance of sources such as soil dust, traffic, oil/coal combustion and road dust for both indoor and outdoor microenvironments. An isolated source in the indoor environment was assigned to environmental tobacco smoke (ETS) with high factor loading of Ce, Cl, I, K, La and Zn. The overall results of our study indicate that the sources of indoor constituents were strongly dependent on outdoor processes except for the ones affected by independent sources such as ETS. PRACTICAL IMPLICATIONS: An improved understanding of the factors affecting the indoor PM2.5 concentration levels can lead to the development of an efficient management strategy to control health risks from exposure to indoor PM2.5 and related toxic components. A comparison of our comprehensive data sets indicated that most indoor PM2.5 and associated elemental species were strongly enriched by indoor source activities along with infiltration of ambient outdoor air for a naturally ventilated building.     

Spatial distribution and temporal variation of metals in the vicinity of a municipal solid waste incinerator after a modernization of the flue gas cleaning systems of the facility

In June 1994 and 1997, the concentrations of a number of elements were determined in soil and herbage samples collected in the vicinity of a municipal solid waste incinerator (MSWI) (Tarragona, Catalonia, Spain). In August 1997, an adaptation to the EU legislation on pollutant emissions from the stack was carried out to the incinerator. In June 1999, soil and herbage samples were collected again at the same sampling points and the levels of arsenic (As), cadmium (Cd), chromium (Cr), lead (Pb), manganese (Mn), mercury (Hg), nickel (Ni) and vanadium (V) were measured by ICP-MS or AAS with graphite furnace. The results are compared with those obtained in the 1994 and 1997 surveys. In the period 1997-1999, the only significant changes in soil levels corresponded to Cd and Pb, with decreases of 21.0% and 53.5%, respectively. In vegetation, only Mn levels showed a significant reduction, which contrasts with the notable increases found in the concentrations of As, Hg and Ni. According to the results of this survey, it seems evident that other metal emission sources in the same area of study are masking the environmental improvements carried out in the MSWI.     

Associations between indoor CO2 concentrations and sick building syndrome symptoms in U.S. office buildings: an analysis of the 1994-1996 BASE study data

Higher indoor concentrations of air pollutants due, in part, to lower ventilation rates are a potential cause of sick building syndrome (SBS) symptoms in office workers. The indoor carbon dioxide (CO2) concentration is an approximate surrogate for indoor concentrations of other occupant-generated pollutants and for ventilation rate per occupant. Using multivariate logistic regression (MLR) analyses, we evaluated the relationship between indoor CO2 concentrations and SBS symptoms in occupants from a probability sample of 41 U.S. office buildings. Two CO2 metrics were constructed: average workday indoor minus average outdoor CO2 (dCO2, range 6-418 ppm), and maximum indoor 1-h moving average CO2 minus outdoor CO2 concentrations (dCO2MAX). MLR analyses quantified dCO2/SBS symptom associations, adjusting for personal and environmental factors. A dose-response relationship (p < 0.05) with odds ratios per 100 ppm dCO2 ranging from 1.2 to 1.5 for sore throat, nose/sinus, tight chest, and wheezing was observed. The dCO2MAX/SBS regression results were similar.     

Solid respirometry to characterize nitrification kinetics: a better insight for modelling nitrogen conversion in vertical flow constructed wetlands

We developed an original method to measure nitrification rates at different depths of a vertical flow constructed wetland (VFCW) with variable contents of organic matter (sludge, colonized gravel). The method was adapted for organic matter sampled in constructed wetland (sludge, colonized gravel) operated under partially saturated conditions and is based on respirometric principles. Measurements were performed on a reactor, containing a mixture of organic matter (sludge, colonized gravel) mixed with a bulking agent (wood), on which an ammonium-containing liquid was applied. The oxygen demand was determined from analysing oxygen concentration of the gas passing through the reactor with an on-line analyzer equipped with a paramagnetic detector. Within this paper we present the overall methodology, the factors influencing the measurement (sample volume, nature and concentration of the applied liquid, number of successive applications), and the robustness of the method. The combination of this new method with a mass balance approach also allowed determining the concentration and maximum growth rate of the autotrophic biomass in different layers of a VFCW. These latter parameters are essential inputs for the VFCW plant modelling.     

Mobilization of lead from human bone tissue during pregnancy and lactation--a summary of long-term research

The skeleton is potential endogenous source of lead during pregnancy and lactation. We have undertaken a longitudinal investigation into the mobilization of lead from the human maternal skeleton to determine whether lead is mobilized from the maternal skeleton during pregnancy and lactation, and if so, when and how much is released. Subjects in the study were migrants to Australia (n=15) whose skeletal lead isotopic composition (endogenous lead) was different to that prevailing in the Australian environment (exogenous lead). This migrant cohort was compared with 6 multi-generational Australian controls. Biological and environmental samples were taken pre-pregnancy where possible, throughout pregnancy and postpartum for at least 6 months. Newly-born infants of the migrant and Australian mothers were monitored for 6 months. Blood lead concentrations for the migrant mothers ranged from 1.5 to 20 microg/dl (geometric mean 2.8) and for Australian mothers ranged from 1.9 to 4.3 microg/dl (geometric mean 2.9). There was minimal change in lead isotopic composition of the Australian pregnant controls although there were increases of approximately 40% in blood lead concentration in 3 of 6 cases during the postpartum period and from 0 to 12% in the other 3. In the migrant pregnant subjects, the geometric mean skeletal lead contribution to blood lead using the isotopic composition was approximately 33% (range 10-88%) for 14 subjects using a revised estimate for exogenous lead. Skeletal contribution to blood lead during the postpartum period was significantly greater than during pregnancy (P<0.001). The skeletal contributions to blood lead are higher and the changes are more consistent in those subjects who conceived within 100 days of arrival in Australia compared with those who conceived longer than 100 days. In the migrant subjects, changes in blood lead concentration during pregnancy and postpartum varied from subject to subject with an overall 20% increase; the increases during the postpartum period were greater than during pregnancy (P<0.001). It was estimated that the amount of maternal skeletal lead mobilized during pregnancy and transferred to the infant via cord blood averaged approximately 79%. The increased skeletal contribution to blood lead is attributed to a low daily calcium intake of approximately 500 mgCa/day, a condition which was present in both migrant and Australian subjects. An ongoing clinical trial is providing a new cohort with calcium supplements. A summary of other aspects of the study is included and covers: additional flux released from the skeleton during pregnancy and postpartum; XRF bone lead results; urinary excretion of lead during pregnancy and postpartum; dietary contribution to blood lead in female adults and children; comparison of rates of exchange of lead in blood of newly-born infants and mothers; relationships of lead in breast milk to lead in blood, urine and diet of the infant and mother; changes in blood lead after cessation of breastfeeding; urinary lead isotopes during pregnancy and postpartum indicate no preferential partitioning of endogenous lead into plasma; a comparison of some aspects of the nonhuman primate and human pregnancy studies.