The weight method: a new screening method for estimating pesticide deposition from knapsack sprayers in developing countries

Investigations of occupational and environmental risk caused by the use of agrochemicals have received considerable interest over the last decades. And yet, in developing countries, the lack of staff and analytical equipment as well the costs of chemical analyses make it difficult, if not impossible, to monitor pesticide contamination and residues in humans, air, water, and soils. A new and simple method is presented here for estimation of pesticide deposition in humans and soil after application. The estimate is derived on the basis of water mass balance measured in a given number of high absorbent papers under low evaporative conditions and unsaturated atmosphere. The method is presented as a suitable, rapid, low cost screening tool, complementary to toxicological tests, to assess occupational and environmental exposure caused by knapsack sprayers, where there is a lack of analytical instruments. This new method, called the “weight method”, was tested to obtain drift deposition on the neighbouring field and the clothes of the applicator after spraying water with a knapsack sprayer in one of the largest areas of potato production in Colombia. The results were confirmed by experimental data using a tracer and the same set up used for the weight method. The weight method was able to explain 86% of the airborne drift and deposition variance.     

Effects of selected pharmaceutically active compounds on the ammonia oxidizing bacterium Nitrosomonas europaea

Pharmaceutically active compounds (PhACs) are commonly found in wastewater influent. However, little research has focused on determining their impact on fundamental processes in wastewater treatment such as nitrogen removal. In this study, focus was placed on 4 commonly occurring PhACs (ketoprofen, naproxen, carbamazepine and gemfibrozil). Their effect was ascertained in the ammonia oxidizing bacterium (AOB), Nitrosomonaseuropaea in terms of membrane integrity and nitrite production. These PhACs were shown to inhibit nitrite production at concentrations of 1 and 10 μM while no effect was observed at 0.1 μM. The maximum observed nitrification inhibition was 25%, 29%, 22% and 26% for ketoprofen, naproxen, carbamazepine and gemfibrozil, respectively. A decrease in the live/dead ratio ranging from 10% to 16% suggests that these PhACs affect membrane integrity in N.europaea. The difference in nitrite production between PhACs treated cells and non PhAC treated controls was still significant following washing suggesting that inhibition is irreversible. Finally, nitrite production when adjusted to the live fraction of cells was also found to decrease suggesting that PhACs inhibited the activity of surviving cells. These results suggest that the presence of PhACs may affect AOB activity and may impact nitrogen removal, a key function in wastewater treatment. Follow up studies with additional AOB and in mixed culture are needed to further confirm these results.     

Identification and quantification of new polybrominated dimethoxybiphenyls (PBDMBs) in marine mammals from Australia

Marine mammals from Queensland, Australia, are bioaccumulating elevated concentrations of a range of polybrominated natural products. In this study, we detected three new polybrominated dimethoxybiphenyls (PBDMBs) in the blubber of selected marine mammal samples which were identified as 2,6'-dimethoxy-3,3',5-tribromobiphenyl (2,6'-diMeO-BB 36), 2,2'-dimethoxy-3,3'-dibromobiphenyl (2,2'-diMeO-BB 36), and 6,6'-dimethoxy-3,3'-dibromobiphenyl (6,6'-diMeO-BB 11). These three PBDMBs are structurally related to the known natural product 2,2'-dimethoxy-3,3',5,5'-tetrabromobiphenyl (2,2'-diMeO-BB 80). In the first part of this study, 2,2'-diMeO-BB 80 was photochemically debrominated under UV irradiation. This resulted in seven of eight possible mono- to triBDMBs as debromination products. In the second part of this study, the structure of all PBDMBs debromination products was investigated. This was supported by synthesis of two diBDMB and one triBDMB via bromination and subsequent methylation of 2,2'-biphenyldiol. Structures of the remaining PBDMBs were tentatively assigned by considering the retention times, mass spectra and amounts formed during UV irradiation of 2,2'-diMeO-BB 80 . In the third part of this study, blubber of marine mammals from Australia was analysed for PBDMBs using gas chromatography in combination with electron ionization mass spectrometry (GC/EI-MS) in the selected ion monitoring mode. In these samples, 2,2'-diMeO-BB 80 was found at concentrations of 200-1800ngg(-1) lipid weight (lw). The latter represents the highest concentration reported for this compound in environmental samples. 6,6'-diMeO BB 11, 2,2'-diMeO BB 36, and 2,6'-diMeO BB 36 were present at approximately 7ngg(-1) lipids, or 0.43-1.5% of diMeO-BB 80. No further PBDMBs were detected in the samples. The di- and triBDMBs identified in marine mammal blubber have not been reported as natural products. They may represent either new natural products or transformation products of 2,2'-diMeO-BB 80.     

Environmental risks of farmed and barren alkaline coal ash landfills in Tuzla, Bosnia and Herzegovina

The disposal of coal combustion residues (CCR) has led to a significant consumption of land in the West Balkan region. In Tuzla (Bosnia and Herzegovina) we studied previously soil-covered (farmed) and barren CCR landfills including management practises, field ageing of CCR and the transfer of trace elements into crops, wild plants and wastewaters. Soil tillage resulted in mixing of cover soil with CCR. Medicago sativa showed very low Cu:Mo ratios (1.25) which may cause hypocuprosis in ruminants. Total loads of inorganic pollutants in the CCR transport water, but not pH ( approximately 12), were below regulatory limits of most EU countries. Arsenic concentrations in CCR transport water were <2microgl(-1) whereas reductive conditions in an abandoned landfill significantly enhanced concentrations in leachates (44microgl(-1)). The opposite pattern was found for Cr likely due to large initial leaching of CrVI. Public use of landfills, including farming, should be based on a prior risk assessment due to the heterogeneity of CCR.     

Using certified timber extraction to benefit jaguar and ecosystem conservation

The jaguar Panthera onca requires large areas of relatively intact habitats containing adequate amounts of prey to survive. Since a substantial portion of jaguar range occurs outside of strict protected areas, there is a need for economic incentives for habitat conservation, which carefully managed selective logging can provide. Forest Stewardship Council and Pan European Forest Council certifications intended to regulate wood extraction to maintain the ecological functions of forests require evidence of biodiversity and ecosystem conservation. We draw on twelve surveys across four countries and a range of biomes to present evidence that adequate logging management can maintain jaguar populations, but that they are at risk without efficient control of secondary impacts of access and hunting. Where resident, the presence of jaguars can serve as an indication that the ecological requirements of certified timber extraction are being met. We present a gradient of rigor for monitoring, recommending cost-effective options.     

Biochar and earthworm effects on soil nitrous oxide and carbon dioxide emissions

Biochar is the product of pyrolysis produced from feedstock of biological origin. Due to its aromatic structure and long residence time, biochar may enable long-term carbon sequestration. At the same time, biochar has the potential to improve soil fertility and reduce greenhouse gas (GHG) emissions from soils. However, the effect of biochar application on GHG fluxes from soil must be investigated before recommendations for field-scale biochar application can be made. A laboratory experiment was designed to measure carbon dioxide (CO) and nitrous oxide (NO) emissions from two Irish soils with the addition of two different biochars, along with endogeic (soil-feeding) earthworms and ammonium sulfate, to assist in the overall evaluation of biochar as a GHG-mitigation tool. A significant reduction in NO emissions was observed from both low and high organic matter soils when biochars were applied at rates of 4% (w/w). Earthworms significantly increased NO fluxes in low and high organic matter soils more than 12.6-fold and 7.8-fold, respectively. The large increase in soil NO emissions in the presence of earthworms was significantly reduced by the addition of both biochars. biochar reduced the large earthworm emissions by 91 and 95% in the low organic matter soil and by 56 and 61% in the high organic matter soil (with and without N fertilization), respectively. With peanut hull biochar, the earthworm emissions reduction was 80 and 70% in the low organic matter soil, and only 20 and 10% in the high organic matter soil (with and without N fertilization), respectively. In high organic matter soil, both biochars reduced CO efflux in the absence of earthworms. However, soil CO efflux increased when peanut hull biochar was applied in the presence of earthworms. This study demonstrated that biochar can potentially reduce earthworm-enhanced soil NO and CO emissions. Hence, biochar application combined with endogeic earthworm activity did not reveal unknown risks for GHG emissions at the pot scale, but field-scale experiments are required to confirm this.     

Biochar and hydrochar effects on greenhouse gas (carbon dioxide, nitrous oxide, and methane) fluxes from soils

With a growing world population and global warming, we are challenged to increase food production while reducing greenhouse gas (GHG) emissions. We studied the effects of biochar (BC) and hydrochar (HC) produced via pyrolysis or hydrothermal carbonization, respectively, on GHG fluxes in three laboratory incubation studies. In the first experiment, ryegrass was grown in sandy loam mixed with equal amounts of a nitrogen-rich peanut hull BC, compost, BC+compost, double compost, or no addition (control); wetting-drying cycles and N fertilization were applied. Biochar with or without compost significantly reduced NO emissions and did not change the CH uptake, whereas ryegrass yield was significantly increased. In the second experiment, 0% (control) or 8% (w/w) of BC (peanut hull, maize, wood chip, or charcoal) or 8% HC (beet chips or bark) was mixed into a soil and incubated at 65% water-holding capacity (WHC) for 140 d. Treatments included simulated plowing and N fertilization. All BCs reduced NO emissions by ～60%. Hydrochars reduced NO emissions only initially but significantly increased them after N fertilization to 302% (HC-beet) and 155% (HC-bark) of the control emissions, respectively. Large HC-associated CO emissions suggested that microbial activity was stimulated and that HC was less stable than BC. In the third experiment, nutrient-rich peanut hull BC addition and incubation over 1.5 yr at high WHCs did not promote NO emissions. However, NO emissions were significantly increased with BC after NHNO addition. In conclusion, BC reduced NO emissions and improved the GHG-to-yield ratio under field-relevant conditions. However, the risk of increased NO emissions with HC addition must be carefully evaluated.     

Ultrasensitive determination of carbendazim in water and orange juice using a carbon paste electrode

A carbon paste electrode was used for the electrochemical quantification of carbendazim in water and orange juice samples. Carbendazim oxidation on the electrode surface was found to be controlled by adsorption. The novel electrochemical procedure for carbendazim quantification employed differential pulse voltammetry using a carbon paste electrode under optimal conditions. Carbendazim oxidation currents were linear at concentrations of 2.84 to 45.44 µg L^?1, with a limit of detection of 0.96 µg L^?1. The proposed method was applied to carbendazim quantification in ultrapurified water, river water, and orange juice. Recovery rates in water and orange juice samples were in the 97%–101% range, indicating that the method can be employed to determine carbendazim in these matrices, with advantages including shorter analysis time and lower cost than routine methods such as chromatography or spectroscopy. The electrode showed good reproducibility, remarkable stability, and especially good surface renewability by simple mechanical polishing. The recovery rates observed were highly concordant with those obtained for high-performance liquid chromatography, having a relative standard deviation of less than 1.3%.     

Environmental quality assessment of reservoirs impacted by Hg from chlor-alkali technologies: case study of a recovery

Mercury (Hg) pollution legacy of chlor-alkali plants will be an important issue in the next decades with the planned phase out of Hg-based electrodes by 2025 within the Minamata convention. In such a context, the present study aimed to examine the extent of Hg contamination in the reservoirs surrounding the Oltchim plant and to evaluate the possible improvement of the environmental quality since the closure of its chlor-alkali unit. This plant is the largest chlor-alkali plant in Romania, which partly switched to Hg-free technology in 1999 and definitely stopped the use of Hg electrolysis in May 2012. Total Hg (THg) and methylmercury (CH₃Hg) concentrations were found to decrease in the surface waters and sediments of the reservoirs receiving the effluents of the chlor-alkali platform since the closure of Hg units. Hence, calculated risk quotients (RQ) indicated no adverse effect of Hg for aquatic organisms from the ambient water exposure. RQ of Hg in sediments were mostly all higher than 1, showing important risks for benthic organisms. However, ecotoxicity testing of water and sediments suggest possible impact of other contaminants and their mixtures. Hg hotspots were found in soils around the platform with RQ values much higher than 1. Finally, THg and CH₃Hg concentrations in fish were below the food safety limit set by the WHO, which contrasts with previous measurements made in 2007 revealing that 92 % of the studied fish were of high risk of consumption. Discontinuing the use of Hg electrodes greatly improved the surrounding environment of chlor-alkali plants within the following years and led to the decrease environmental exposure to Hg through fish consumption. However, sediment and soil still remained highly contaminated and problematic for the river reservoir management. The results of this ecological risk assessment study have important implications for the evaluation of the benefits as well as limits of the Minamata Convention implementation.