An appraisal of soil diffuse contamination in an industrial district in northern Italy

Soil diffuse contamination is one the major soil threats, especially in regions with a high population density and strong industrialization. In this work agricultural, natural, and periurban soils of an Italian Province (858 km(2)) were sampled and analyzed. Overall, 140 samples were taken at two depths and analyzed for 10 trace elements, 13 rare earth elements and for organic contaminants (PCBs, PCDDs and PAHs). The aim of this work was to obtain an appraisal of soil diffuse contamination in a large Italian Province by applying and validating available tools to quantify background values and evaluate the intensity of contamination. Data were processed, background values estimated, and enrichment and contamination factors calculated. For some contaminants the results allowed a discrimination between natural or anthropic-derived contaminants. Some contaminants revealed clear trends of enrichment in function of the land use (in particular for periurban soils). REEs were found to mostly derive from parent material. The results obtained in this study show the importance of merging the quantification of contaminants with the elaboration of indices of contamination. These require an accurate quantification of background values to be able to discriminate the anthropic contribution. Enrichment factor resulted to be more accurate than contamination factor but it cannot be applied to organic contaminants and requires a careful selection of the reference element to be adopted. This study revealed that some contaminants - Sb, Sn, Pb, and organic contaminants - can be used as tracers of diffuse contamination, and should be therefore always included in similar studies.     

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.     

Application of Automated Mass Spectrometry Deconvolution and Identification Software for Pesticide Analysis in Surface Waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

Contamination status of arsenic and other trace elements in drinking water and residents from Tarkwa, a historic mining township in Ghana

This study was conducted to assess the contamination status of 22 trace elements, especially As in water and residents in Tarkwa, a historic mining town in Ghana. Drinking water and human urine samples were collected from Tarkwa in addition to control samples taken from Accra, the capital of Ghana in March, 2004. Concentrations of As and Mn in some drinking water samples from Tarkwa were found above the WHO drinking water guidelines posing a potential health risk for the people. A potential health risk of As and Mn is a concern for the people consuming the contaminated water in this area. No significant difference of As concentrations in human urine between mining town (Tarkwa) and control site (Accra) was observed. Although As concentrations in drinking water in Tarkwa were low, urinary As levels were comparable to those reported in highly As-affected areas in the world. These results suggest the presence of other sources of As contamination in Ghana. This is the first study on multi-elemental contamination in drinking water and human from a mining town in Ghana.     

Organic tracers identification as a convenient strategy in industrial landfills monitoring

Today, a significant environmental problem is due to the presence of industrial landfills, some of them old, which can release toxic compounds into the environment (Chemosphere 42 (2001) 415; Chemosphere 31 (1995) 3455). The identification of directly linked to the leachate tracers of contamination in the wells around the landfills, as early markers of a potential risk for the environment and/or man, is a good strategy for an early evaluation of contamination. Our protocol developed for wells water characterization is based on solid phase extraction combined with GC-MS and HPLC-MS/MS.In this way a list of organic contaminants of a specific industrial landfill is obtained, giving a solid basis also for the risk assessment. Here we present some specific examples and the use of these pollutants for environmental monitoring.     

Analytical improvements of hybrid LC-MS/MS techniques for the efficient evaluation of emerging contaminants in river waters: a case study of the Henares River (Madrid, Spain)

Purpose  

Instrumental capabilities and software tools of modern hybrid mass spectrometry (MS) instruments such as high-resolution mass spectrometry (HRMS), quadrupole time-of-flight (QTOF), and quadrupole linear ion trap (QLIT) were experimentally investigated for the study of emerging contaminants in Henares River water samples.     

TiO2光催化技术处理饮用水微污染及杀灭微生物的研究

光催化处理饮用水微量污染物以及在饮用水消毒和杀菌方面的研究是近年来研究的热点.本文论述了 TiO2光催化处理饮用水中的微量卤代物、腐殖质、微生物代谢产物,以及杀灭细菌、真菌和病毒等微生物的研究进展.探讨了光催化杀灭微生物的作用机制,最后对该研究领域的发展方向提出建议和展望.     

Spatial variability of metallic and organic contamination of anguilliform fish in New Caledonia

New Caledonia is one of the main hot spots of biodiversity on the planet. Large amounts of contaminants are discharged into the lagoon as a result of increasing anthropogenic activities such as intense mining, urbanization, and industrialization. Concentrations of 14 trace elements and 26 persistent organic pollutants (POPs: PCBs and pesticides) were measured in the muscles of two anguilliform fish species, over a coast to barrier reef gradient in two lagoon areas differently exposed to anthropic disturbances. This study emphasizes the high trace element contamination status of anguilliform fish and also highlights slight but perceptible organic pollution. The contamination extends throughout the lagoon, from coast to barrier reef, even in areas remote from emission points. High levels of trace elements, especially those linked to mining activities (i.e., Co, Cr, Fe, Mn, and Ni), were detected in coastal sites. Furthermore, the large dispersion of most POPs throughout the entire lagoon poses the question of their potential toxicity on marine organisms from numerous habitats. Our results underline the need for long-term monitoring of various contaminants over large spatial and time scales.     

Sorption and degradation of pharmaceuticals and personal care products (PPCPs) in soils

Pharmaceuticals and personal care products (PPCPs) are one class of the most urgent emerging contaminants, which have drawn much public and scientific concern due to widespread contamination in aquatic environment. Most studies on the environmental fate and behavior of PPCPs have focused on nonsteroidal anti-inflammatory drugs. Some other compounds with high concentrations were less mentioned. In this study, sorption and degradation of five selected PPCPs, including bisphenol A (BPA), carbamazepine (CBZ), gemfibrozil (GFB), octylphenol (OP), and triclosan (TCS) have been investigated using three different soils. Sorption isotherms of all tested PPCPs in soils were well described by Freundlich equation. TCS and OP showed moderate to strong sorption, while the sorption of GFB and CBZ in soils was negligible. Degradation of PPCPs in three soils was generally fitted first-order exponential decay model, with half-lives (t _1/2) varying from 9.8 to 39.1 days. Sterilization could prolong the t _1/2 of PPCPs in soil, indicating that microbial activity played an important role in the degradation of these chemicals in soils. Degradation of PPCPs in soils was also influenced by the soil organic carbon (f _oc) contents. Results from our data show that sorption to the soils varied among the different PPCPs, and their sorption affinity on soil followed the order of TCS > OP > BPA > GFB > CBZ. The degradation of the selected PPCPs in soil was influenced by the microbial activity and soil type. The poor sorption and relative persistence of CBZ suggest that it may pose a high leaching risk for groundwater contamination when recycled for irrigation.     

Screening of endocrine-disrupting phenols, herbicides, steroid estrogens, and estrogenicity in drinking water from the waterworks of 35 Italian cities and from PET-bottled mineral water

We investigated contamination by endocrine-disrupting chemicals in drinking water from 35 major Italian cities and five popular Italian brands of bottled mineral water. The quality of Italian drinking water was assessed by combing chemical analysis with bioassay to quantify specific estrogenic contaminants and to characterize the actual biological effect of the mixture of chemicals present in drinking water including the contribution of not targeted compounds. The selected contaminants were natural and synthetic steroid estrogens, alkylphenols and bisphenol A, linuron, triazine herbicides, and their metabolites. A specific analytical method was developed based on solid phase extraction of 1 L of water and concentration to 100 μL for quantification by electrospray ionization liquid chromatography tandem mass spectrometry, achieving quantification limits of 0.05–0.36 ng/L for herbicides and 0.64–7.70 ng/L for steroids and phenols. No steroid estrogens were detected in any of the samples, while bisphenol A and nonylphenols were detected in the ranges of 0.82–102.00 and 10.30–84.00 ng/L respectively. Herbicides and their degradation products, when present, were found from slightly above the quantification limits up to 49.91 ng/L, mainly from cities in northern Italy. Chemical analyses were complemented by the performance of a bioassay for the determination of the estrogenic activity in the extracts based on the transactivation of estrogen receptor α-transfected reporter HeLa-ERE-Luciferase-Neomycin cell line. Activity was generally low with maximum estrogenicity of 13.6 pg/L estradiol equivalents.     

Influence of seasonal climate differences on the pharmaceutical,hormone and personal care product removal efficiency of a drinking water treatment plant

The potential presence of pharmaceuticals, hormones and personal care products in drinking water supplies has raised concerned over the efficiency with which these substances are removed by water treatment processes. In this work, we analyzed samples of raw, unprocessed water collected in different periods and found them to contain higher levels of these contaminants in the colder periods (viz. 12–314 ng L⁻¹ in autumn and winter as compared to 8–127 ng L⁻¹ in spring and summer) as a result of their biodegradation being favoured by high temperatures and solar irradiance. We also assessed the efficiency with which these contaminants are removed from drinking water by a water treatment plant operating in south-eastern Spain. Preoxidation with potassium permanganate and chloramination with sodium hypochlorite in the presence of highly concentrated ammonia were found to be the treatment steps most markedly contributing to the removal of pharmaceuticals, hormones and personal care products from drinking water (especially in the warmer periods, where these contaminants were completely removed from the water). By contrast, water treated in the colder periods (autumn and winter) still contained small amounts of ibuprofen and carbamazepine (0.09–0.5 ng L⁻¹) which, however, accounted for less than 0.2% of their original concentrations in the water prior to treatment.     

水中痕量有机磷农药的高效液相色谱/质谱分析

农药对饮用水以及饮用水源的污染在西方发达国家是一项极为关注的课题。有机磷农药作为农药中的一大类,至今仍是世界上生产和使用最多的农药品种。因此,饮用水以及饮用水源中痕量有机磷农药残留的状况受到人们关注。水中痕量有机磷农药的分析方法正在不断地改进,针对ＧＣ／ＭＳ测定某些有机磷农药时存在热分解以及在气相色谱柱上发生吸附的不足。结合高灵敏度、高选择性的质谱鉴定器,本文主要介绍最新的ＨＰＬＣ／ＡＰＩＭＳ方法在水中痕量有机磷农药测定方面的进展和应用。     

Simultaneous analysis of 50 pesticides in water samples by solid phase extraction and GC-MS

A multiresidue analysis of 50 pesticides has been developed as a rapid screening method for organic contaminants in water samples. Solid phase extraction was accomplished with two adsorbents in a single column. Simultaneous analysis was performed with gas chromatography-mass spectrometry (GC-MS). The limits of detection for each pesticide are at sub-ppb levels. This method was used to check contamination of water from the Adige river (Northern Italy).     

Fate and behaviour of phenanthrene in the natural and artificial soils

For the assessment of contaminated soils ecotoxicological tests are used to estimate the bioavailability of contaminants in soil samples. Terrestrial tests reveal the habitat function of soils, and parameters applied in tests involving microorganisms include respiration activity and potential ammonium oxidation. For such tests, the threshold values needed to assess the results have already been established in guidelines ISO 17155 and ISO 15685. In this paper, we discuss about the respiration activity and potential ammonium oxidation results obtained from a wide variety of soils with different physico-chemical properties and levels of contamination. These results show that microbial respiration and potential ammonium oxidation have different sensitivities to various classes of contaminants. We demonstrated that both organic and inorganic contaminants influence potential ammonium oxidation, whereas microbial respiration is predominantly affected by biodegradable organic contaminants. These differences might be useful for more detailed assessments of soil contamination, leading to different recommended actions depending on which parameter is affected.     

Trace analysis of dissolved polychlorinated organic compounds in the water of the Yangtse River (Nanjing, China)

Eighteen organochlorine contaminants from the water samples of the Yangtse River have been qualitatively and quantitatively analyzed. The analysis of polychlorinated organic compounds (PCOCs) extracted by C18 Solid Phase Extract (SPE) was performed using HP6890 gas chromatograph coupled by ECD detector. The analytical results demonstrate that the analytical methods are reliable based on the fact that most of the recoveries for the targeted compounds are 60-90%. Most of the concerned contaminants, i.e. chlorinated pesticides and PCBs were found in the water samples of the Yangtse River, but their concentration was very low, <2.97 ng l(-1), which is far less than 1 microg l(-1)--the standard of drinking water of China. It is apparent that the PCOCs were in high concentration during the dry season, and in low concentration during the rainy season. The situation of PCOCs contamination in the water of the Yangtse River in 1999 was greatly improved in comparison with 10 years ago.     

Membrane introduction/laser photoionization time-of-flight mass spectrometry

Two-photon resonance enhanced multiphoton ionization (REMPI) has been shown to be a unique ionization method for mass spectrometry, exhibiting both high sensitivity and chemical selectivity. Because REMPI is a gas-phase method, its applications have been limited either to direct analysis of vapor phase samples, or in conjunction with an initial laser desorption or other vaporization step. We describe here for the first time a combination of membrane introduction mass spectrometry (MIMS) and REMPI with time-of-flight mass spectrometry (TOF-MS), which allows for the direct analysis of trace amounts of organic compounds in water samples. The objective of our research was the detection of very low levels of aromatic contaminants, particularly benzene, toluene, and xylene (BTX), in aqueous solutions without interference due to the water. We have measured limits of detection (LOD) for selected aromatics in water below 1 part-per-trillion with an averaging time of less than 10 s using a continuous sample flow.     

Fecal coliforms, caffeine and carbamazepine in stormwater collection systems in a large urban area

Water samples from streams, brooks and storm sewer outfall pipes that collect storm waters across the Island of Montréal were analyzed for caffeine, carbamazepine and fecal coliforms. All samples contained various concentrations of these tracers, indicating a widespread sanitary contamination in urban environments. Fecal coliforms and caffeine levels ranged over several orders of magnitude with a modest correlation between caffeine and fecal coliforms (R² value of 0.558). An arbitrary threshold of 400 ng caffeine L⁻¹ allows us to identify samples with an elevated fecal contamination, as defined by more than 200 colony-forming units per 100 mL (cfu 100 mL⁻¹) of fecal coliforms. Low caffeine levels were sporadically related to high fecal coliform counts. Lower levels of caffeine and fecal coliforms were observed in the brooks while the larger streams and storm water discharge points contained over ten times more. The carbamazepine data showed little or no apparent correlation to caffeine. These data suggest that this storm water collection system, located in a highly urbanized urban environment, is widely contaminated by domestic sewers as indicated by the ubiquitous presence of fecal contaminants as well as caffeine and carbamazepine. Caffeine concentrations were relatively well correlated to fecal coliforms, and could potentially be used as a chemical indicator of the level of contamination by sanitary sources. The carbamazepine data was not significantly correlated to fecal coliforms and of little use in this dataset.     

Determination of pharmaceuticals, personal care products, and pesticides in surface and treated waters: method development and survey

Water is fundamental to the existence of life since it is essential to a series of activities, such as agriculture, power generation, and public and industrial supplies. The residual water generated by these activities is released into the environment, reaches the water systems, and becomes a potential risk to nontarget organisms. This paper reports the development and validation of a quantitative method, based on solid-phase extraction and liquid chromatography tandem mass spectrometry, for the simultaneous analysis of 18 pharmaceuticals and personal care products (PPCPs) and 33 pesticides in surface and drinking waters. The accuracy of the method was determined by calculating the recoveries, which ranged from 70 to 120 % for most pesticides and PPCPs, whereas limits of quantification ranged from 0.8 to 40 ng/L. After the validation step, the method was applied to drinking and surface waters. Pesticides and PPCPs were found in concentrations lower than 135.5 ng/L. The evaluation of different water sources with regard to contamination by pesticides and PPCPs has been quite poor in southern Brazil.     

Experimental evaluation of PCDD/Fs and PCBs release and mass balance of a WTE plant

The behaviour of waste incineration plants with respect to organic toxic trace contaminants such as PCDDs, PCDFs and, to a minor extent, PCBs, is still a matter of concern for the public opinion and the decision makers. It is therefore very important, first, to evaluate the release of these organic toxic trace contaminants in the environment during waste incineration, not only through the stack gas emission but also with the solid and liquid residues, and then to compare the total release with the input through the treated waste in order to assess the plant behaviour as a “sink” rather than a “source” of organic toxic trace contaminants. The experimental investigation carried out on an Italian full scale incineration plant has shown a total 17 PCDD/Fs and 12 dioxin-like PCBs release of 5.5-27 μg WHO-TEQ per tonne of treated waste and an input flux of 1.6-44 μg WHO-TEQ per tonne of waste, with the difference between the input and the output fluxes rather small and the plant behaviour toward organic trace toxic contaminants in average neutral. Results are compared with similar evaluations conducted in the last decade on a number of waste-to-energy (WTE) plants operating in Italy.     

Continental bottled water assessment by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry (SBSE-GC-MS/MS)

This study was aimed to determine the presence of 69 organic contaminants in 77 representative bottled waters collected from 27 countries all over the world. All water samples were contained in polyethylene terephthalate bottles. Target compounds were (1) environmental contaminants (including 13 polycyclic aromatic hydrocarbons (PAHs), 31 pesticides including organochlorine (OCPs), organophosphorus, and pyrethroids; 7 polychlorinated biphenyls (PCBs); and 7 triazines) and (2) plasticizers (including 6 phthalates and 5 other compounds). Samples were analyzed by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry. PAHs, OCPs, PCBs, and triazines, which are indicators of groundwater pollution, were not detected in most of the samples, except for naphthalene (0.005–0.202 μg/L, n?=?16). On the other hand, plastic components were detected in 77 % of the samples. Most frequently detected compounds were dimethyl phthalate and benzophenone at concentrations of 0.005–0.125 (n?=?41) and 0.014–0.921 (n?=?32), respectively. Levels detected are discussed in terms of contamination origin and geographical distribution. Target compounds were detected at low concentrations. Results obtained showed the high quality of bottled water in the different countries around the world.