Survey of phthalates, alkylphenols, bisphenol A and herbicides in Spanish source waters intended for bottling

Background, aim and scope

Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination.

Materials and methods

Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed.

Results and discussion

Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77?C124?%) and limits of quantification were between 0.0004 and 0.029???g/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018???g/L for octylphenol to 0.970???g/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115???g/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds.

Conclusions

Target compounds were detected in a very low concentration and only in very few samples. This indicates the good quality of source waters intended for bottling and the effectiveness of the protection measures adopted in Spain. None of the samples analysed exceeded the maximum legislated levels for drinking water both in Spain and in the European Union.     

Carbon Storage in Soil Size Fractions Under Two Cacao Agroforestry Systems in Bahia, Brazil

Shaded perennial agroforestry systems contain relatively high quantities of soil carbon (C) resulting from continuous deposition of plant residues; however, the extent to which the C is sequestered in soil will depend on the extent of physical protection of soil organic C (SOC). The main objective of this study was to characterize SOC storage in relation to soil fraction-size classes in cacao (Theobroma cacao L.) agroforestry systems (AFSs). Two shaded cacao systems and an adjacent natural forest in reddish-yellow Oxisols in Bahia, Brazil were selected. Soil samples were collected from four depth classes to 1 m depth and separated by wet-sieving into three fraction-size classes (>250 μm, 250–53 μm, and <53 μm)—corresponding to macroaggregate, microaggregate, and silt-and-clay size fractions—and analyzed for C content. The total SOC stock did not vary among systems (mean: 302 Mg/ha). On average, 72% of SOC was in macroaggregate-size, 20% in microaggregate-size, and 8% in silt-and-clay size fractions in soil. Sonication of aggregates showed that occlusion of C in soil aggregates could be a major mechanism of C protection in these soils. Considering the low level of soil disturbances in cacao AFSs, the C contained in the macroaggregate fraction might become stabilized in the soil. The study shows the role of cacao AFSs in mitigating greenhouse gas (GHG) emission through accumulation and retention of high amounts of organic C in the soils and suggests the potential benefit of this environmental service to the nearly 6 million cacao farmers worldwide.     

Mortality due to haematological cancer in cities close to petroleum refineries in Spain

Controversy exists as to whether working or living in the vicinity of a petroleum refinery (RF) increases the risk of haematological cancer (HC). The European Pollutant Release and Transfer Register obliges petroleum refineries to notify their emissions of toxic substances which include carcinogenic substances. Our objective is to determine if living in the proximity of an RF is associated with a greater risk of mortality due to HC in the census tracts (CTs) of the Spanish cities of Bilbao, Cartagena, Castellón, La Coruña, Huelva, and Santa Cruz de Tenerife. This is an ecological study of mortality in the years 1996–2007 which includes 968 CTs with 1,263,371 inhabitants. Exposure has been measured as the distance from the centroid of each CT to the RF. The Besag–York–Mollié autoregressive spatial model has been fitted by R-INLA to estimate the relative risk (RR) and 95 % credible intervals (95 % CrI) for distance in quintiles. The most distant quintile has been taken as the reference. A total of 2,574 persons died of HC. The distances from the CTs to RFs ranged from 0.5 to 22.5 km (median?=?7.6 km). All of the RRs for the quintiles of distances in Huelva were greater than 1. Statistically significant excess risk was shown in Cartagena in the nearest CT (1.8 to 6.8 km; RR?=?1.43, 95 % CrI 1.02 to 2.02). Radial effects have not been detected between the CT of residence and the petroleum RF in mortality due to HC in any of the cities.     

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

Adsorption of As(III) on chitosan-Fe-crosslinked complex (Ch-Fe)

It was reported the adsorption of As(III) on the surface of the chitosan-Fe-crosslinked complex. Theoretical correlation of the experimental equilibrium adsorption data for As(III)/Ch-Fe system is best explained by the non-linearized form Langmuir-Freundlich isotherm model. At optimum conditions, pH 9.0, the maximum adsorption capacity, calculated using the Langmuir-Freundlich isotherm model was 13.4 mg g⁻¹. The adsorption kinetics of As(III) onto Ch-Fe are described by the pseudo-first-order kinetic equation. The results of the Mössbauer spectroscopy showed that there is no redox process on the surface of the adsorbent.     

Determination of lipid peroxidation and cytotoxicity in calcium, magnesium, titanium and hectorite (SHCa-1) suspensions

This paper reports data on the relative ability of CaO, CaCl₂, MgO, MgCl₂, TiO₂, and hectorite (SHCa-1) to induce oxidative stress (as determined by lipid peroxidation, LP) in biological matrices. The effectiveness of structural (oxide form) versus soluble Ca and Mg to induce LP is compared. An assessment on cytotoxicity as affected by soluble and structural Ca, Mg, TiO₂ and SHCa-1 is also addressed. LP was screened and monitored using the Thiobarbituric Acid Reactive Substances (TBARS). The extent of TBARS production was found to vary with the type and initial concentration of the soluble or structural cation, Ca or Mg respectively. Obtained results showed higher magnitude values for the latter set of experiments. In the presence of TiO₂ no significant TBARS production was detected pointing out a negligible effect of TiO₂ on LP. At solid concentrations ca. 100 ppm, CaO appears to be more effective than SHCa-1 to induce LP. By contrast at ca. 25 ppm, MgO appears to be more effective than the clay mineral. The SHCa-1 LP-inducing activity has been proven to closely relate to structural Ca. The prevalence of mechanisms that may induce LP but not cytotoxicity (as determined by cell growth inhibition) was also addressed. Results on cell growth inhibition as affected by soluble and structural Ca, Mg, TiO₂ and hectorite provide evidence to support that structural Ca or Mg brings about significantly higher variations than soluble Ca.     

Use of recycled fine aggregate in concretes with durable requirements

The use of construction waste materials as aggregates for concrete production is highly attractive compared to the use of non-renewable natural resources, promoting environmental protection and allowing the development of a new raw material. Several countries have recommendations for the use of recycled coarse aggregate in structural concrete, whereas the use of the fine fraction is limited because it may produce significant changes in some properties of concrete. However, during the last decade the use of recycled fine aggregates (RFA) has achieved a great international interest, mainly because of economic implications related to the shortage of natural sands suitable for the production of concrete, besides to allow an integral use of this type of waste. In this study, the durable behaviour of structural concretes made with different percentage of RFA (0%, 20%, and 30%) is evaluated. Different properties related to the durability of concretes such as absorption, sorptivity, water penetration under pressure, and carbonation are determined. In addition, the results of compressive strength, static modulus of elasticity and drying shrinkage are presented. The obtained results indicate that the recycled concretes have a suitable resistant and durable behaviour, according to the limits indicated by different international codes for structural concrete.     

Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.     

Atmospheric fate of non-volatile and ionizable compounds

A modified version of the Multimedia Activity Model for Ionics MAMI, including two-layered atmosphere, air-water interface partitioning, intermittent rainfall and variable cloud coverage was developed to simulate the atmospheric fate of ten low volatility or ionizable organic chemicals. Probabilistic simulations describing the uncertainty of substance and environmental input properties were run to evaluate the impact of atmospheric parameters, ionization and air-water (or air-ice) interface enrichment.The rate of degradation and the concentration of OH radicals, the duration of dry and wet periods, and the parameters describing air-water partitioning (K_AW and temperature) and ionization (pK_a and pH) are the key parameters determining the potential for long range transport. Wet deposition is an important removal process, but its efficiency is limited, primarily by the duration of the dry period between precipitation events.Given the underlying model assumptions, the presence of clouds contributes to the higher persistence in the troposphere because of the capacity of cloud water to accumulate and transport non-volatile (e.g. 2,4-D) and surface-active chemicals (e.g. PFOA). This limits the efficiency of wet deposition from the troposphere enhancing long-range transport.     

Integrated hydrologic–economic decision support system for groundwater use confronting climate change uncertainties in the Tunuyán River basin,Argentina

This study presents an integrated hydrologic–economic model as decision support system for groundwater use and incorporates uncertainties of climate change. The model was developed with the Vensim software (Ventana Systems) for system dynamic simulations. The software permitted the integration of economic variables along with hydrologic variables, in a unified format with the aim of evaluating the economic impacts of climate change on arid environments. To test the model, we applied it in one of the upper Tunuyán River sub-basin, located in the Mendoza Province (Argentina), where irrigation comes from groundwater. The model defines the best mix of crops and the total land use required to maximize the total river sub-basin monetary income, considering as a limit the amount of water that does not exceed the natural annual aquifer recharge. To estimate the impacts of climatic changes, four scenarios were compared: the business as usual (with the number of existing wells) in a dry year with a temperature increase of 4 °C; the business as usual in a wet year with an increase in temperature of 1.1 °C; an efficient use of wells in a dry year and a temperature increase of 4 °C and an efficient use of wells in a wet year with a temperature increase of 1.1 °C. Outputs calculated by the model were: land use per crop, total sub-basin net benefit, total sub-basin water extraction, water extraction limit depending on river discharge and total number of wells required to irrigate the entire area. Preliminary results showed that the number of existing wells exceeded the optimized number of wells required to sustainably irrigate the entire river sub-basin. Results indicated that in an average river discharge year, if wells were efficiently used, further rural development would be possible, until the limit of 350 million m³ of water extraction per year was reached (650 million m³ for a wet year and 180 million m³ for a dry year). The unified format and the low cost of the software license make the model a useful tool for Water Resources Management Institutions, particularly in developing countries.