Engineered nanomaterials in rivers--exposure scenarios for Switzerland at high spatial and temporal resolution

Probabilistic material flow analysis and graph theory were combined to calculate predicted environmental concentrations (PECs) of engineered nanomaterials (ENMs) in Swiss rivers: 543 river sections were used to assess the geographical variability of nano-TiO₂, nano-ZnO and nano-Ag, and flow measurements over a 20-year period at 21 locations served to evaluate temporal variation. A conservative scenario assuming no ENM removal and an optimistic scenario covering complete ENM transformation/deposition were considered. ENM concentrations varied by a factor 5 due to uncertain ENM emissions (15%-85% quantiles of ENM emissions) and up to a factor of 10 due to temporal river flow variations (15%-85% quantiles of flow). The results indicate highly variable local PECs and a location- and time-dependent risk evaluation. Nano-TiO₂ median PECs ranged from 11 to 1′623 ng L⁻¹ (conservative scenario) and from 2 to 1′618 ng L⁻¹ (optimistic scenario). The equivalent values for nano-ZnO and nano-Ag were by factors of 14 and 240 smaller.     

Can arbuscular mycorrhizal fungi improve grain yield, As uptake and tolerance of rice grown under aerobic conditions?

The effects of arbuscular mycorrhizal fungi (AMF) - Glomus intraradices and G. geosporum on arsenic (As) and phosphorus (P) uptake by lowland (Guangyinzhan) and upland rice (Handao 502) were investigated in soil, spiked with and without 60 mg As kg⁻¹. In As-contaminated soil, Guangyinzhan inoculated with G. intraradices or Handao 502 inoculated with G. geosporum enhanced As tolerance, grain P content, grain yield. However, Guangyinzhan inoculated with G. geosporum or Handao 502 inoculated with G. intraradices decreased grain P content, grain yield and the molar ratio of grain P/As content, and increased the As concentration and the ratio of grain/straw As concentration. These results show that rice/AMF combinations had significant (p < 0.05) effects on grain As concentration, grain yield and grain P uptake. The variation in the transfer and uptake of As and P reflected strong functional diversity in AM (arbuscular mycorrhizal) symbioses.     

Development of competitive immunoassays to hydroxyl containing fungicide metabolites

This paper describes the isolation of monoclonal antibodies and the development of competitive immunoassays to pesticide metabolites of the fungicides imazalil, carbendazim and thiabendazole. The metabolite specific hydroxyl residues were used as the reactive group with which to link the metabolite to the carrier proteins Keyhole Limpet Haemocyanin (KLH) and Bovine Serum Albumin (BSA). In each case immune responses in mice were raised and monoclonal antibodies were produced. Antibodies were developed into competitive ELISAs to the appropriate metabolite. The antibody raised to a metabolite of imazalil was optimised into a competitive ELISA format which had an assay IC50 of 7.5 μg/L and a limit of detection (LOD) of 1.1 μg/L. A single antibody isolated against the metabolite of carbendazim had assay IC50s of 3.2 and 2.7 μg/L for the metabolites of carbendazim and thiabendazole respectively with an LOD of 0.38 μg/L for both. These sensitive immunoassays may have application in the monitoring of human exposure to these fungicide residues either by occupational or non-occupational routes.     

Ecological impacts of the N-viro biosolids land-application for wild blueberry (Vaccinium angustifolium. Ait) production in Nova Scotia

Land application of biosolids from processed sewage sludge may deteriorate soil, water, and plants. We investigated the impact of the N-Viro biosolids land-application on the quality of the soil water that moved through Orthic Humo-Ferric Podzols soil of Nova Scotia (NS) at the Wild Blueberry Research Institute, Debert, NS Canada. In addition, the response of major soilproperties and crop yield was also studied. Wild blueberry (Vaccinium angustifolium. Ait) was grown under irrigated and rainfed conditions in 2008 and 2009. Four experimental treatments including (i) NI: N-Viro irrigated, (ii) NR: N-Viro rainfed, (iii) FI: inorganic fertilizer irrigated, and (iv) FR: inorganic fertilizer rainfed (control) were replicated 4 times under randomized complete block design. Soil samples were collected at the end of each year and analyzed for changes in cation exchange capacity (CEC), soil organic matter (SOM), and pH.Soil water samples were collected four times during the study period from the suction cup lysimeters installed within and below crop root zone at 20 and 40 cm depths, respectively. The samples were analyzed for a range of water quality parameters including conductance, hardness, pH, macro- and micronutrients, and the infectious pathogens Escherichia coli (E. coli) and salmonella. Berries were harvested for fruit yield estimates. Irrigation significantly increased CEC during 2008 and the soil pH decreased from 4.93 (2008) to 4.79 (2009). There were significant influences of irrigation, fertilizer, and their interaction, in some cases, on most of the soil water quality parameters except on the infectious bacteria. No presence of E. coli or salmonella were observed in soil and water samples, reflecting the absence of these bacteria in biosolids used in this experiment. Nutrient concentration in the soil water samples collected from the four treatments were higher in the sequence NI > NR > FI > FR. The irrigation treatment had significant effect on the unripe fruit yield. We conclude that the comparable performance of N-Viro biosolids and the increasing prices of inorganic fertilizers would compel farmers to use economically available N-Viro biosolids that, coupled with the supplemental irrigation, did not deteriorate the studied soil properties, soil water quality, and the wild blueberry yield during this experiment.     

Functional redundancy and food web functioning in linuron-exposed ecosystems

An extensive data set describing effects of the herbicide linuron on macrophyte-dominated microcosms was analysed with a food web model to assess effects on ecosystem functioning. We showed that sensitive phytoplankton and periphyton groups in the diets of heterotrophs were gradually replaced by more tolerant phytoplankton species as linuron concentrations increased. This diet shift--showing redundancy among phytoplankton species--allowed heterotrophs to maintain their functions in the contaminated microcosms. On an ecosystem level, total gross primary production was up to hundred times lower in the treated microcosms but the uptake of dissolved organic carbon by bacteria and mixotrophs was less sensitive. Food web efficiency was not consistently lower in the treated microcosms. We conclude that linuron predominantly affected the macrophytes but did not alter the overall functioning of the surrounding planktonic food web. Therefore, a risk assessment that protects macrophyte growth also protects the functioning of macrophyte-dominated microcosms.     

Hexachlorocyclohexane (HCH) as new Stockholm Convention POPs��a global perspective on the management of Lindane and its waste isomers

Purpose

Hexachlorocyclohexane (HCH) isomers (??-, ??- and ??- (Lindane)) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention, and therefore, the legacy of HCH and Lindane production became a contemporary topic of global relevance. This article wants to briefly summarise the outcomes of the Stockholm Convention process and make an estimation of the amount of HCH waste generated and dumped in the former Lindane/HCH-producing countries.

Results

In a preliminary assessment, the countries and the respective amount of HCH residues stored and deposited from Lindane production are estimated. Between 4 and 7 million tonnes of wastes of toxic, persistent and bioaccumulative residues (largely consisting of alpha- (approx. 80%) and beta-HCH) are estimated to have been produced and discarded around the globe during 60 years of Lindane production. For approximately 1.9 million tonnes, information is available regarding deposition. Countries are: Austria, Brazil, China, Czech Republic, France, Germany, Hungary, India, Italy, Japan, Macedonia, Nigeria, Poland, Romania, Slovakia, South Africa, Spain, Switzerland, Turkey, The Netherlands, UK, USA, and former USSR. The paper highlights the environmental relevance of deposited HCH wastes and the related POPs?? contaminated sites and provides suggestions for further steps to address the challenge of the legacy of HCH/Lindane production.

Conclusion

It can be expected that most locations where HCH waste was discarded/stockpiled are not secured and that critical environmental impacts are resulting from leaching and volatilisation. As parties to the Stockholm Convention are legally required to take action to stop further POPs pollution, identification and evaluation of such sites are necessary.     

Effects of the organophosphate insecticide azinphos-methyl on the reproduction and cholinesterase activity of Biomphalaria glabrata

Azinphos-methyl is an organophosphate insecticide used for pest control on a number of food crops in many parts of the world. The snail Biomphalaria glabrata is a freshwater gastropod widely distributed in South America, Central America and Africa. The aim of the present work was to investigate whether azinphos-methyl causes alterations in the reproduction of B. glabrata. To this end, gastropod pigmented specimens were exposed to various concentrations of the insecticide (0.021, 0.5, 2.5, and 5 mg L⁻¹) for either 2 or 14 d. Along 14 d, several reproduction parameters and cholinesterase (ChE) activity were evaluated. In each group, the number of egg masses, the number of eggs per mass, the number of hatchings, the time to hatching, and the survival of the offspring after one month of treatment was evaluated. The results showed that, depending on the concentration and time of exposure, azinphos-methyl induced alterations in the reproduction of B. glabrata. These alterations were mainly represented by a decrease in the number of egg masses, and, in some cases, by a lower number or even the total absence of hatchings. Thus, the gastropods exposed to 2.5 and 5 mg L⁻¹ of azinphos-methyl for 14 d showed ChE inhibitions higher than 35% along time and completely lost their ability to reproduce. On the other hand, exposure to high acute concentrations or exposure to low concentrations for 14 d resulted in ChE inhibition equal to or lower than 35% between 7 and 14 d of treatment and similar alterations in reproduction. These were represented by a decrease in the number of egg masses. At low pestice levels, the number of egg masses and the number of offspring resulted to be more sensitive biomarkers than ChE inhibition. It is concluded that the insecticide azinphos-methyl can cause a decline in the reproductive performance of B. glabrata.     

Magnetic ion exchange treatment of stabilized landfill leachate

Stabilized landfill leachate is characterized by a high concentration of non-biodegradable organic matter, which is similar in chemistry to dissolved organic matter (DOM) in the natural aquatic environment. Magnetic ion exchange (MIEX) resin treatment is well-studied in drinking water for removal of DOM from natural waters. There are fewer studies evaluating MIEX treatment of waste waters, and there is no previous work evaluating MIEX treatment of landfill leachate. This work systematically evaluated MIEX treatment of stabilized landfill leachate and evaluated the results in the context of previous studies of MIEX treatment of natural and waste waters. Five leachates from four landfills were evaluated as a function of MIEX resin dose, mixing time, and regeneration efficiency. MIEX resin removed DOM from landfill leachate, even in the presence of a reported high background concentration of inorganic ions. MIEX resin that was exhausted with leachate DOM was effectively regenerated with a concentrated NaCl solution, and regenerated MIEX resin performed similarly to virgin resin. For a majority of the leachates, the removal trend for MIEX resin was color > UV-absorbing substances > dissolved organic carbon ≈ COD > total nitrogen. Finally, MIEX resin removed a wider range of DOM from leachate than coagulation. The most important contribution of this work is that MIEX treatment of leachate followed very similar trends as MIEX treatment of natural waters, which will allow previous MIEX data to be used to estimate the treatment efficiency of other waste waters.     

Probability of intellectual disability is associated with soil concentrations of arsenic and lead

Background

The association between metals in water and soil and adverse child neurologic outcomes has focused on the singular effect of lead (Pb), mercury (Hg), and arsenic (As). This study describes the complex association between soil concentrations of As combined with Pb and the probability of intellectual disability (ID) in children.

Methods

We used a retrospective cohort design with 3988 mother child pairs who were insured by Medicaid and lived during pregnancy and early childhood in South Carolina between 1/1/97 and 12/31/02. The children were followed until 6/1/08, using computerized service files, to identify the diagnosis of ID in medical records and verified by either school placement or disability service records. The soil was sampled using a uniform grid and analyzed for eight metals. The metal concentrations were interpolated using Bayesian Kriging to estimate concentration at individual residences.

Results

The probability of ID increased for increasing concentrations of As and Pb in the soil. The Odds Ratio for ID, for one unit change in As was 1.130 (95% confidence interval 1.048-1.218) for Pb was 1.002 (95% confidence interval 1.000-1.004). We identified effect modification for the infants based on their birth weight for gestational age status and only infants who were normal size for their gestational age had increased probability of ID based on the As and Pb soil concentrations (OR for As at normal weight for gestational age = 1.151 (95% CI: 1.061-1.249) and OR for Pb at normal for gestational age = 1.002 (95% CI: 1.002-1.004)). For normal weight for gestational age children when As = 22 mg kg⁻¹ and Pb = 200 mg kg⁻¹ the risk for ID was 11% and when As = 22 mg kg⁻¹and Pb = 400 mg kg⁻¹ the probability of ID was 65%.

Conclusion

The probability of ID is significantly associated with the interaction between Pb and As for normal weight for gestational age infants.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.