The impact of point source pollution on shallow groundwater used for human consumption in a threshold country

Many developing and threshold countries rely on shallow groundwater wells for their water supply whilst pit latrines are used for sanitation. We employed a unified strategy involving satellite images and environmental monitoring of 16 physico-chemical and microbiological water quality parameters to identify significant land uses that can lead to unacceptable deterioration of source water, in a region with a subtropical climate and seasonally restricted torrential rainfall in Northern Argentina. Agricultural and non-agricultural sources of nitrate were illustrated in satellite images and used to assess the organic load discharged. The estimated human organic load per year was 28.5 BOD(5) tons and the N load was 7.5 tons, while for poultry farms it was 9940-BOD(5) tons and 1037-N tons, respectively. Concentrations of nitrates and organics were significantly different between seasons in well water (p values of 0.026 and 0.039, respectively). The onset of the wet season had an extraordinarily negative impact on well water due in part to the high permeability of soils made up of fine gravels and coarse sand. Discriminant analysis showed that land uses had a pronounced seasonal influence on nitrates and introduced additional microbial contamination, causing nitrification and denitrification in shallow groundwater. P-well was highly impacted by a poultry farm while S-well was affected by anthropogenic pollution and background load, as revealed by Principal Component Analysis. The application of microbial source tracking techniques is recommended to corroborate local sources of human versus animal origin.     

Modeling the effect of land use/land cover on nitrogen,phosphorous and dissolved oxygen loads in the Velhas River using the concept of exclusive contribution area

Non-point source water pollution is a major problem in most parts of the world, but is also very difficult to quantify and control since it is not easily separated from point sources and can theoretically originate from the whole watershed. In this article, we evaluate the relationship between land use and land cover and four water pollution parameters in a watershed in Southeast Brazil. The four parameters are nitrate, total ammonia nitrogen, total phosphorous, and dissolved oxygen. To help concentrate on non-point source pollution, only data from the wet seasons of the time period (2001–2013) were analysed, based on the fact that precipitation causes runoff which is the main cause of diffuse pollution. The parameters measured were transformed into loads, which were in turn associated with an exclusive contribution area, so that every measuring station could be considered independent. Analyses were also performed on riparian zones of different widths to verify if the effect of the land cover on the water quality of the stream decreases with the increased distance. Pearson correlation coefficients indicate that urban areas and agriculture/pasture tend to worsen water quality (source). Conversely, forest and riparian areas have a reducing effect on pollution (sink). The best results were obtained for total ammonia nitrogen and dissolved oxygen using the whole exclusive contribution areas with determination coefficients better than R²≈0.8. Nitrate and total phosphorous did not produce valid models. We suspect that the transformation delay from total ammonia nitrogen to nitrate might be an important factor for the poor result for this parameter. For phosphorous, we think that the phosphorous sink in the bottom sediment might be the most limiting factor explaining the failure of our models.     

Cadmium and lead in bovine milk in the mining area of the Caudal River (Spain)

The levels of cadmium and lead in 36 raw bovine milk samples were analysed. These samples come from seven farms with a semi-extensive grazing system and were collected between the autumn of 2007 and the winter of 2008. All the farms were located in Asturias (Spain), a zone of great industrial and mining activity in the proximities of the Caudal River. The samples were collected in sterile precleaned polypropylene tubes and frozen until the analysis. After a lyophilization process, the samples were treated with nitric acid and microwave treatment. Cadmium and lead determinations were carried out using inductively coupled plasma mass spectrometry with sensibility under 0.2 ppb for liquid matrix. The lead content was found to vary from 0.71 to 16.06 μg/kg wet weight (w.w.), and the cadmium was lower than 2 μg/kg w.w. The levels of lead in milk are higher in those farms near zones of storage of mining waste depots, thermal power and areas with high levels of traffic. All the values found are in concordance with research carried out at non-polluted areas, and those for the lead are well below the European Union limitations.     

Faecal shield chemical defence is not important in larvae of the tortoise beetle Chelymorpha reimoseri (Chrysomelidae: Cassidinae: Stolaini)

The most frequently investigated defence mechanism among larvae of tortoise beetles is protection by faecal shields, which generally present chemicals that are directly sequestered and/or modified from larval host-plants. In the present work we investigate the tortoise beetle Chelymorpha reimoseri that feeds on the leaves of Ipomoea carnea fistulosa (Convolvulaceae), seeking for the importance of this mechanism to their larvae. We show that 4th instar larvae suffer low predation regardless of the presence of shields in field and laboratory bioassays with ants and chicks. Chloroform extract from larvae without shields provided high protection against predation as shown in bioassays in the field, as well as against chicks, suggesting that C. reimoseri does not rely on the shield for protection. The aqueous extract of the shields did not show activity in such bioassays. The compounds responsible for this protection have yet to be identified, and it remains an open question as to whether they are sequestered from the host plant or de novo biosynthesized. This is the first record of chemical defence in cassidine beetles without the need for faecal shields. These findings indicate that more attention should be paid to chemicals present in the tissues of larvae and/or adults of tortoise beetles; the protective compounds sequestered from host plants or de novo biosynthesized can provide an alternative or complementary strategy against predation in these insects.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Suitability of different salt marsh plants for petroleum hydrocarbons remediation

The suitability of the salt-marsh species Halimione portulacoides, Scirpus maritimus, Juncus maritimus and an association of the last two for remediation of petroleum hydrocarbons (PHC) in soil was investigated. An outdoor laboratory experiment (microcosm-scale) was carried out using contaminated soil collected in a refinery, as a complement of another study carried out in the refinery environment (mesocosm-scale). Soil samples with old contamination (mainly crude oil) and with a mixture of the old and recent (turbine oil) contamination were tested. Studies in both micro- and mesocosm-scale provided results coherent in substance. The presence of S. maritimus caused removal of old contamination which was refractory to natural attenuation (after 7 months of exposure, efficiency was 13% when only old contamination was present and 40% when the soil also contained recent contamination). H. portulacoides (only included in the microcosm-scale study) revealed also potentiality for PHC remediation, although with less efficiency than S. maritimus. Degradation of recent contamination was also faster in the presence of plants (after 7 months: 100% in the presence of S. maritimus vs. 63% in its absence). As these species are common in salt marsh areas in Atlantic coast of Europe, it is probable they will be also useful for recovering coast sediments. In contrast, J. maritimus and association did not reveal capability to remove PHC from soil, the presence of J. maritimus inhibiting the capability of S. maritimus.     

Geochronology of anthropogenic radionuclides in Ribeira Bay sediments, Rio de Janeiro, Brazil

Ribeira Bay is located approximately 130 km south of the city of Rio de Janeiro and receives discharges of liquid effluent from the Angra dos Reis nuclear power plant (NPP) site, where two pressurized water reactors are located. To test whether the presence of anthropogenic radionuclides in sediments in Ribeira Bay could be correlated to the NPP operations, we sampled seven sediment cores and determined accumulation rates and chronologies. Only one sediment core did not exhibit a superficial mixing layer; this sample was used for dating purposes. Cesium-137 and ²⁰⁷Bi were observed in this sediment profile, but their presence was associated with atmospheric fall-out rather than the nearby NPP. The exponential decay of ²¹⁰Pb concentration with sediment layer depth was verified below a superficial mixing layer for all other sediment cores. Calculated accumulation rates ranged from 1.2 mm y⁻¹ in the inner bay to 6.2 mm y⁻¹ close to its entrance.