Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System1

Stoeckel, James A., Jade Morris, Elizabeth Ames, David C. Glover, Michael J. Vanni, William Renwick, and María J. González, 2012. Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System. Journal of the American Water Resources Association (JAWRA) 48(3): 616-634. DOI: 10.1111/j.1752-1688.2011.00633.x Abstract: We used enzyme-linked immunosorbent assay to examine reservoir-mediated shifts in spring to fall exposure of aquatic organisms to the spring atrazine pulse over four years in a Midwestern stream-reservoir system. Peak atrazine concentrations in the major inflowing stream exceeded 10 μg/l in all four years. The reservoir had a beneficial effect in two of four years by diluting atrazine below the 10 μg/l threshold. However, during the other two years, exposure times above 10 μg/l were approximately doubled in the reservoir compared to the major inflowing stream. Thresholds of 3 and 5 μg/l were exceeded during all four years in the reservoir. The uplake and downlake reservoir sites were four to five times more likely to exceed these thresholds and aquatic organisms were subjected to longer exposure times above these thresholds compared to the inflowing stream. Release of elevated atrazine concentrations from the reservoir extended exposure times in the outflowing stream. This effect was most pronounced just below the dam. Aquatic organisms upstream of the reservoir were most likely to experience acute exposures whereas organisms within and immediately downstream of the reservoir were more likely to experience chronic exposures. The ubiquity of reservoirs and the annual spring herbicide flush highlight the importance of considering the presence and relative location of reservoirs when assessing risk to aquatic communities as well as locations of drinking water intakes.     

Bioindication of volatile elements emission by the Puyehue-Cordón Caulle (North Patagonia) volcanic event in 2011

The emission of volatile pollutants from the volcanic eruption of the Puyehue-Cordón Caulle complex (North Patagonia Andean Range) that started in June 4th, 2011, was investigated by bioindication means with the epyphytic fruticose lichen Usnea sp. The elemental composition of pooled samples made up with 10 lichen thalli were analysed by Instrumental Neutron Activation Analysis. Eleven sampling sites were selected within the impacted region at different distance from the volcanic source. Five sites were selected as they were already sampled in a previous study prior to the eruption. Two other new sampling sites were selected from outside the impacted zone to provide non-impacted baseline sites.The elements associated with the lichen incorporation of particulate matter (PM) of geological origin were identified by linear correlation with a geochemical tracer (Sm concentrations). The elements associated with PM uptake were Ce, Eu, Fe, Hf, La, Lu, Na, Nd, Sb, Sc, Se, Ta, Tb, Th, U, and Yb. Arsenic and Cs concentrations showed contributions exceeding the PM fraction in sites near the volcanic centre, also higher than the baseline concentrations, which could be associated with permanent emissions from the geothermal system of the Puyehue-Cordón Caulle complex. The lichen concentrations of Ba, Ca, Co, Hg, K, Rb, Sr, and Zn were not associated with the PM, not showing higher concentrations in the sites nearby the volcanic source or respect to the baseline values either. Therefore, there is no indication of the emission of volatile forms of these elements in the lichen records. The lichen records only identified Br volatile emissions associated with the Puyehue-Cordón Caulle complex eruption in 2011.     

Pesticide residue dynamics in passion fruits: Comparing field trial and modelling results

We evaluated the exposure to pesticides from the consumption of passion fruits and subsequent human health risks by combining several methods: (i) experimental field studies including the determination of pesticide residues in/on passion fruits, (ii) dynamic plant uptake modelling, and (iii) human health risk assessment concepts. Eight commonly used pesticides were applied onto passion fruits cultivated in Colombia. Pesticide concentrations were measured periodically (between application and harvest) in whole fruits and fruit pulp. Measured concentrations were compared with predicted residues calculated with a dynamic and crop-specific pesticide uptake model, namely dynamiCROP. The model accounts for the time between pesticide application and harvest, the time between harvest and consumption, the amount of spray deposition on plant surfaces, uptake processes, dilution due to crop growth, degradation in plant components, and reduction due to food processing (peeling). Measured and modelled residues correspond well (r² = 0.88-0.99), with all predictions falling within the 90% confidence interval of the measured values. A mean error of 43% over all studied pesticides was observed between model estimates and measurements. The fraction of pesticide applied during cultivation that is eventually ingested by humans is on average 10⁻⁴-10⁻⁶, depending on the time period between application and ingestion and the processing step considered. Model calculations and intake fractions via fruit consumption based on experimental data corresponded well for all pesticides with a deviation of less than a factor of 2. Pesticide residues in fruits measured at recommended harvest dates were all below European Maximum Residue Limits (MRLs) and therefore do not indicate any violation of international regulatory thresholds.     

Evaluation of effectiveness of EDTA and sodium thiosulfate in removing metal toxicity toward sea urchin embryo-larval applying the TIE

Since the development of the TIE (Toxicity Identification and Evaluation) in 1988 it has been assumed that the capacity of EDTA and sodium thiosulfate to complex some metals, and thus remove their toxicity, can be applied to both freshwater and seawater ecotoxicological tests and the results subsequently interpreted. However, it is now known that there is a wide variability in the extent of this complexation. In this context, the removal of toxicity caused by the presence of Hg²⁺, Cd²⁺, Cu²⁺, Cr⁶⁺, Zn²⁺, Ni²⁺, Pb²⁺, Ag¹⁺ and Se²⁺, through metal complexation by EDTA and sodium thiosulfate, in relation to the performance of embryo-larval tests with the sea urchin Arbacia lixula was investigated. It was observed that EDTA was capable of removing the toxicity of Pb²⁺, Zn²⁺ and Cu²⁺ while sodium thiosulfate only reduced the toxicity of Ag¹⁺. Compared to the complexation observed in freshwater ecotoxicological tests, the complexing agents used in this study (EDTA and sodium thiosulfate) have a lower capacity to complex metals in the marine ecotoxicological test with A. lixula.     

Toxicity persistence in runoff and soil from experimental soybean plots following insecticide applications

Persistence of toxicity in runoff water and soil was investigated in experimental soybean plots subjected to successive runoff events following pesticide application. Runoff events were produced by irrigation using a sprinkler system. The pesticides applied were cypermethrin and endosulfan, which are widely used in soy production in Argentina. Toxicity tests were performed on two abundant components of the regional fauna, the amphipod Hyalella curvispina and the fish Cnesterodon decemmaculatus. Runoffs from two pesticide applications were assayed at different stages of the growing season: an early application when the soil was almost bare and a late one close to harvest, when the ground was covered by vegetation and just before soy leaves fell. Toxicity to H. curvispina in runoff ceased almost one month after the early application of the two pesticides, while it persisted for over three months after the late application. Soil toxicity to H. curvispina and runoff toxicity to C. decemmaculatus followed the same pattern. Higher temperatures and solar radiation are likely to have enhanced insecticide degradation after the early application. Lower temperatures and solar radiation in combination with increased organic matter from litter probably contributed to the longer persistence of toxicity recorded after the late application, as compared with the early application. Cypermethrin caused no mortality to C. decemmaculatus after the early application, while endosulfan toxicity persisted for almost four months after the late one.     

Fifteen years of monitoring of POPs in the breast milk, Czech Republic, 1994–2009: trends and factors

Background, aim and scope

The breast milk has been recommended to carry out as a monitoring tool for effectiveness evaluation of the Stockholm Convention on Persistent Organic Pollutants (POPs). Polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloro-ethane (DDT) and its metabolites (DDX), hexachlorbenzene (HCB) and isomers of hexachlocyklohexane (HCHs) have been monitored in the breast milk of nursing mothers in the Czech Republic since 1994 as a part of The Environmental Health Monitoring System. Knowledge about long-term POPs distribution and accumulation in the human body is crucial to understanding uptake, degradation and subsequent effects as well as to conduct risk assessments. The main aim of this study is to evaluate 15-years long-term trends of selected POPs in human milk in the Czech Republic and to elucidate the questionnaire information about the age, parity and social habits, to the final concentrations. This effectiveness evaluation of POPs restriction is quite precisely after 15-years monitoring campaigns.

Materials, methods and results

The human milk samples (4,753 samples) were analysed for a number of chlorinated organic chemicals including PCBs and selected chlorinated pesticides (OCPs, HCB, HCHs, DDX). The relative change of concentration per year for all chemicals was analysed. The remaining percentages of POPs in breast milk in comparison to 1994 are also expressed. Czech population half-lives of POPs in breast milk, derived from either linear or exponential models were computed.

Conclusions and perspectives

The long-term data indicates a continuation of a decreasing trend of POPs concentrations on breast milk. Our study did not confirm lactation and parity as an important outflux resulting in the decrease in concentrations in mothers, which is in the antagonism with most of the studies. The higher BMI was associated with higher amounts of HCB and lower amounts of higher chlorinated PCBs. The results confirm the effectiveness of restrictions of POPs usage in the Czech Republic. This ongoing long-term study is very useful tool for parametric effectiveness evaluation of Stockholm Convention.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

A new bioseed for determination of wastewater biodegradability: analysis of the experimental procedure

A new bioassay proposed in the patent P201300029 was applied to a pre-treated wastewater containing a mixture of commercial pesticides to simulate a recalcitrant industrial wastewater in order to determine its biodegradability. The test uses a mixture of standardized inoculum of the lyophilized bacteria Pseudomonas putida with the proper proportion of salts and minerals. The results highlight that biodegradation efficiency can be calculated using a gross parameter (chemical oxygen demand (COD)) which facilitates the biodegradability determination for routine water biodegradability analysis. The same trend was observed throughout the assay with the dehydrated and fresh inoculums, and only a difference of 5 % in biodegradation efficiency (E _f) was observed. The obtained results showed that the P. putida biodegradability assay can be used as a commercial test with a lyophilized inoculum in order to monitor the ready biodegradability of an organic pollutant or a WWTP influent. Moreover, a combination of the BOD₅/COD ratio and the P. putida biodegradability test is an attractive alternative in order to evaluate the biodegradability enhancement in water pre-treated with advanced oxidation processes (AOPs).     

Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.