Comprehensive estimate of the theoretical maximum daily intake of pesticide residues for chronic dietary risk assessment in Argentina

A chronic dietary risk assessment for pesticide residues was conducted for four age groups of the Argentinian population following the procedure recommended by the WHO. The National Theoretical Maximum Daily Intake (NTMDI) for 308 pesticides was calculated for the first time, using the Maximum Residue Limits (MRLs) from several Argentinean regulations and food consumption data from a comprehensive National Nutrition and Health Survey. The risk was estimated by comparing the TMDI with the Acceptable Daily Intakes (ADI) identified by various sources. Furthermore, for each of the compounds with a TMDI >65% of the ADI, a probabilistic analysis was conducted to quantify the probability of exceeding the ADI. In this study 27, 22, 10, and 6 active ingredients (a.i.) were estimated to exceed the 100% of the ADI for the different population groups: 6–23 month-old children, 2–5 year-old children, pregnant women, and 10–49 year-old women, respectively. Some of these ADI-exceeding compounds (carbofuran, diazinon, dichlorvos, dimethoate, oxydemeton-methyl and methyl bromide) were found in all four of these groups. Milk, apples, potatoes, and tomatoes were the foods that contributed most to the intake of these pesticides. The study is of primary importance for the improvement of risk assessment, regulations, and monitoring activities.     

Environment polluting conventional chemical control compared to an environmentally friendly IPM approach for control of diamondback moth, <Emphasis Type="Italic">Plutella xylostella</Emphasis> (L.), in China: a review

The diamondback moth, Plutella xylostella, is recognized as a widely distributed destructive insect pest of Brassica worldwide. The management of this pest is a serious issue, and an estimated annual cost of its management has reached approximately US$4 billion. Despite the fact that chemicals are a serious threat to the environment, lots of chemicals are applied for controlling various insect pests especially P. xylostella. An overreliance on chemical control has not only led to the evolution of resistance to insecticides and to a reduction of natural enemies but also has polluted various components of water, air, and soil ecosystem. In the present scenario, there is a need to implement an environmentally friendly integrated pest management (IPM) approach with new management tactics (microbial control, biological control, cultural control, mating disruption, insecticide rotation strategies, and plant resistance) for an alternative to chemical control. The IPM approach is not only economically beneficial but also reduces the environmental and health risks. The present review synthesizes published information on the insecticide resistance against P. xylostella and emphasizes on adopting an alternative environmentally friendly IPM approach for controlling P. xylostella in China.     

The effects and the toxicity increases caused by bicarbonate,chloride, and other water components during the UV/TiO<Subscript>2</Subscript> degradation of oxazaphosphorine drugs

The influences of HCO₃ ^?, Cl^?, and other components on the UV/TiO₂ degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2? in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO₂ loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO₃ ^? in the UV/TiO₂/HCO₃ ^? system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of ?CO₃ ^? in the system. The results also showed that ?CO₃ ^? likely induces a preferred ketonization pathway. Besides the inorganic anions HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO₃ ^? or Cl^? during UV/TiO₂ treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.     

Design of water quality monitoring networks with two information scenarios in tropical Andean basins

Design and redesign of water quality monitoring networks were evaluated for two similarly sized watersheds in the tropical Andes via optimization techniques using geographic information system technology (GIS) and a matter-element analysis of 5-day biological oxygen demand (BOD₅) and total suspended solids (TSS). This resulted in a flexible, objectively based design for a 1128-km² watershed without prior water quality data (La Miel River), and a network redesign of a 1052-km² watershed with historical water quality monitoring (Chinchiná River). Monitoring design for the undocumented basin incorporated mathematical expressions for physical, anthropological, and historical factors—and was based on clear objectives for diagnosis and intervention of water pollution. Network redesign identified network redundancy, which resulted in a 64% reduction in the number of water quality monitoring stations along the channel, and a 78% reduction of stations throughout the basin. Most tropical drainage basins throughout the world have little to no prior water quality data. But even in well-studied drainage basins like the Chinchiná River, which is among the most thoroughly studied basins in Colombia, redesign of historical and existing monitoring networks will become a standard tool to advance the restoration of polluted surface waters, not only in Colombia, but also throughout the world.     

Assessment and potential sources of metals in the surface sediments of the Yellow River Delta,Eastern China

The Yellow River Delta is the most intact estuary wetland in China and suffers from great pressure of metals. Seventy-seven surface sediment samples were collected in the delta, and contents of Cu, Pb, Cd, Cr, Zn, Ni, and Mn were analyzed by inductively coupled plasma spectrometry and those of Hg and As by atomic fluorescence spectrometry. The results showed that means of metal contents (ppm, dry weight) were as follows: Hg, 0.04; Cr, 61.72; Cu, 20.97; Zn, 60.73; As, 9.47; Pb, 21.91; Cd, 0.12; Ni, 27.24; and Mn, 540.48. 43.8% of Hg and 14.3% of Cd were from the allogenic source while others from the authigenic source. The results of the geoaccumulation indexes appeared that 6.5% of sites from the estuarine and the Gudao areas were moderately polluted by Hg. All ecological risk index values of Hg and 37.7% of Cd were more than 40, which were the main factors of strongly and moderately potential ecological risks of 37.7% of sites in the delta. High Cd contents may be due to the alkaline conditions of the delta and the unreasonable management of the farmland, while the abnormal distribution of Hg to the wet or dry deposition and the erosion of the seawater. It was suggested to monitor Hg content in the atmosphere of the Yellow River Delta. The results were expected to update the pollution status of metals in the delta and created awareness of preserving the sound condition of the Yellow River Delta.     

Urinary levels of phthalate metabolites and associations with demographic characteristics in Korean adults

The objective of this study is to assess human exposure to phthalates and its associations with demographic characteristics of the subjects in the Korean National Human Biomonitoring Survey. The subjects aged between 18 and 69 were selected through nationwide stratified sampling. A total of 1874 urine samples were collected and stored at ?20 °C until measurement for ten selected metabolites of phthalates (MnBP, MiBP, MBzP, MCHP, MnOP, MEHP, MEOHP, MEHHP, MiNP, and MiDP) using high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). The difference in the level of urinary phthalate metabolites by the characteristics of the subjects was tested for statistical significance using SAS Surveyreg procedure. The coefficients and standard errors from multiple linear regressions were exponentiated to estimate the adjusted proportional change (APC) and 95% CIs compared with a referent level. The proportion of data above LOQ was less than 20% for MCHP, MnOP, MiNP, and MiDP. Geometric means of creatinine-adjusted concentrations (unit: μg/g creatinine) of six other phthalate metabolites among Korean adults were 41.7 (95% CI 39.6–43.9) for MnBP, 17.1 (95% CI 16.1–18.1) for MiBP, 15.7 (95% CI 14.4–17.1) for MBzP, 8.65 (95% CI 8.10–9.22) for MEHP, 17.5 (95% CI 16.8–18.3) for MEOHP, and 38.1 (95% CI 36.2–40.2) for MEHHP. Urinary level of phthalates tended to be higher among subjects with older age, females, and those with vigorous daily physical activity and tended to be lower among drinkers and those with higher income. Our results suggest that the level of phthalate exposure is significant among Korean adults and thus warrants further studies to identify major source and route of exposure to phthalates.     

Investigation of low-level <Superscript>242</Superscript>Pu contamination on nutrition disturbance and oxidative stress in <Emphasis Type="Italic">Solanum tuberosum</Emphasis> L.

Plutonium associated with higher molecular weight molecules is presumed to be poorly mobile and hardly plant available. In our present study, we investigate the uptake and effects of Pu treatments on Solanum tuberosum plants in amended Hoagland medium at concentrations of [²⁴²Pu] = 100 and 500 nm, respectively. We found a direct proof of oxidative stress in the plants caused by these rather low concentrations. For the confirmation of oxidative stress, we explored the production of nitric oxide (NO) and hydrogen peroxide (H₂O₂) by epifluorescence microscopy. Oxidative stress markers like lipid peroxidation and superoxide radicals (O₂ ^??) are monitored through histochemical analysis. The biochemical parameters i.e. chlorophyll and carotenoids are measured as an indicator of cellular damage in the tested plants including the enzymatic parameters such as catalase and glutathione reductase. From our work, we conclude that Pu in low concentration has no significant effects on the uptake of many trace and macroelements. In contrast, the content of O₂ ^?? , malondialdehyde (MDA), and H₂O₂ increases with increasing Pu concentration in the solution, while the opposite effects was found for NO, catalase, and glutathione reductase. These findings prove that even low concentration of Pu regulates ROS production and generate oxidative stress in S. tuberosum L.     

Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.     

Dynamic of submicrometer particles in urban environment

Many studies show that particle toxicity increases with decreasing their size, emphasizing the role of submicrometric particles, in particular of ultrafine particles (<100 nm). In fact, particles greater than 2.5 μm are quickly removed through dry and wet deposition on the timescale of hours whereas submicrometer particles may reside in atmosphere for weeks, penetrate in indoor environment, and be long-range transported. High aerosol size resolution measurements are important for a correct assessment of the deposition efficiency in the human respiratory system, and time resolution is another important requisite. Starting from such considerations, time-resolved aerosol particle number size distributions have been measured in downtown Rome. Fast Mobility Particle Sizer (FMPS) and Scanning Mobility Particle Sizer (SMPS) measurements have been carried out at the INAIL’s Pilot Station, located in downtown Rome, in an area characterized by high density of autovehicular traffic. The two instruments have allowed to investigate deeply the urban aerosol in the range of 5.6–560 and 3.5–117 nm, respectively. In particular, the FMPS measurements have confirmed the interpretation about the transition phenomena in the time interval of few seconds, timescale typically associated with the emission of gasoline and diesel engines. In downtown Rome, the hourly average size distribution is bimodal or trimodal with maxima at about 5–15, 20–30, and 70–100 nm. Particle formation in the nucleation mode was associated to freshly emitted autovehicular exhaust.