Perfluorinated acids as novel chemical tracers of global circulation of ocean waters

Perfluorinated acids (PFAs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are global environmental contaminants. The physicochemical properties of PFAs are unique in that they have high water solubilities despite the low reactivity of carbon-fluorine bond, which also imparts high stability in the environment. Because of the high water solubilities, the open-ocean water column is suggested to be the final sink for PFOS and PFOA. However, little is known on the distribution of PFAs in the oceans around the world. Here we describe the horizontal (spatial) and vertical distribution of PFAs in ocean waters worldwide. PFOS and PFOA concentrations in the North Atlantic Ocean ranged from 8.6 to 36pg l(-1) and from 52 to 338pg l(-1), respectively, whereas the corresponding concentrations in the Mid Atlantic Ocean were 13-73pg l(-1) and 67-439pg l(-1). These were completely different from the surface waters of the South Pacific Ocean and the Indian Ocean (overall range of <5-11pg l(-1) for PFOS and PFOA). Vertical profiles of PFAs in the marine water column were associated with the global ocean circulation theory. Vertical profiles of PFAs in water columns from the Labrador Sea reflected the influx of the North Atlantic Current in surface waters, the Labrador Current in subsurface waters, and the Denmark Strait Overflow Water in deep layers below 2000m. Striking differences in the vertical and spatial distribution of PFAs, depending on the oceans, suggest that these persistent acids can serve as useful chemical tracers to allow us to study oceanic transportation by major water currents. The results provide evidence that PFA concentrations and profiles in the oceans adhere to a pattern consistent with the global "Broecker's Conveyor Belt" theory of open ocean water circulation.     

Atrazine removal by ozonation processes in surface waters

Atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazinedyl-2,4-diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continuously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O3/H2O2 process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O3/H2O2 and O3/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

The formation of singlet oxygen in surface waters

The photochemical formation of singlet oxygen in some Dutch surface waters has been investigated using the method developed by Zepp (1). However, when monitoring the consumption of oxygen beside that of 2,5-dimethylfuran (DMF), the compound added to chemically snare singlet oxygen, it was found that appreciable, but varying parts of DMF were used up by secondary reactions leading largely to the same products, viz. cis- and trans-diacetylethylene. When taking the oxygen consumption as a measure for the singlet oxygen production on the basis of the stoichiometry of the primary reaction, a fair correlation between the singlet oxygen production and the total organic carbon (TOC) content was found for this selection of Dutch surface water samples. The steady-state concentrations of singlet oxygen determined in this way were about one order of magnitude lower than those found by Zepp (1) and by Zafiriou (2).     

Atrazine removal by ozonation processes in surface waters

Abstract

Atrazine (6‐chloro‐N‐ethyl‐N'‐isopropyl‐1,3,5‐triazinedyl‐2,4‐diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O₃/H₂O₂ process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O₃/H₂O₂ and O₃/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

Field calibration of surface: a model of agricultural chemicals in surface waters

Agricultural chemicals sporadically occur at detectable levels in the surface waters of intensively farmed watersheds. HSPF, a previously released model of agricultural chemicals in surface water, had been used to predict concentrations which were much higher (10 X) than those actually observed during monitoring studies. A new model, SURFACE, is described here which is much simpler than HSPF and gives better predictions of surface water concentrations. SURFACE uses PRZM, an EPA model, to calculate edge-of-field runoff losses and simple hydraulic routing algorithms to determine concentrations at the bottom of large river basins. In water systems sampled during 1985 and 1986, SURFACE predictions of annualized mean concentrations for alachlor, atrazine, cyanazine and metolachlor were within 0.09 ppb half of the time.     

Field calibration of surface: A model of agricultural chemicals in surface waters

Abstract

Agricultural chemicals sporadically occur at detectable levels in the surface waters of intensively farmed watersheds. HSPF, a previously released model of agricultural chemicals in surface water, had been used to predict concentrations which were much higher (10 X) than those actually observed during monitoring studies. A new model, SURFACE, is described here which is much simpler than HSPF and gives better predictions of surface water concentrations. SURFACE uses PRZM, an EPA model, to calculate edge‐of‐field runoff losses and simple hydraulic routing algorithms to determine concentrations at the bottom of large river basins. In water systems sampled during 1985 and 1986, SURFACE predictions of annualized mean concentrations for alachlor, atrazine, cyanazine and metolachlor were within 0.09 ppb half of the time.     

Organochlorine pesticides in the surface waters of Northern Greece

A survey undertaken in Northern Greece has shown that organochlorine pesticides are present in the surface waters. Surface water samples have been collected seasonally from four rivers and five lakes for a period of two years. Solid-phase extraction followed by gas chromatographic techniques with electron capture detection was used for the determination of the compounds. The most commonly encountered organochlorine pesticides in surface waters were the isomers of hexachlorocyclohexane, aldrin, dieldrin and endosulfan sulfate. In some cases the concentrations detected were higher than the qualitative target levels set by the European Union, especially for hexachlorocyclohexane and aldrin. The occurrence of these compounds in Greek surface waters can be attributed to intense agricultural activity as well as to transboundary pollution.     

Aluminium speciation in surface waters from a Welsh upland area

The complete aluminium speciation of surface waters from an acidified catchment, during dry weather and during storm episodes, is obtained. For the first time, estimates of adsorbed aluminium (Al(ad)) are reported together with other aluminium species. Al(ad) is calculated from the difference between monomeric aluminium content before and after separation of suspended solids by filtration (0.015 microm pore diameter). This fraction was very significant (Al(ad) >; 40 microg litre(-1)) for samples with high suspended solids content (ss >; 20 mg litre(-1)) collected during storm episodes. Plots of pAl(3+) versus pH for samples collected during dry weather are approximated by a straight line, close to the solubility line of synthetic gibbsite, and have a slope of 2.5, which suggests that these samples were saturated with respect to gibbsite. The cloud of pAl(3+) versus pH points for samples from storm episodes has a near zero slope, and shows a significant degree of undersaturation with respect to synthetic gibbsite. Various mechanisms of aluminium mobilisation are discussed.     

Occurrence and source of brominated organic compounds in surface waters

Monitoring of organic halogen compounds, measured as adsorbable organically bound bromine (AOBr), in an eutrophic lake, which is influenced by treated waste water, revealed repeatedly high concentrations of organobromine compounds in late summer, whereas five times lower values were measured during the rest of the year. It was possible to reproduce the in situ observed AOBr increase in the laboratory. Batch experiments were performed with lake water from two different lakes and an algae culture. It could be shown that the AOBr production is not limited to strong waste water influenced lakes. Furthermore, the AOBr formation requires light and the presence of algae, and thus is most probably biotic in nature. A low content of nutrients favours the formation of organic bromine compounds. To our knowledge this is the first report about the seasonally occurrence of naturally produced organic bromine compounds in lakes/surface waters.     

Volatile organic compounds in the surface waters of northern Greece

An investigation into the occurrence of volatile organic compounds (VOCs) was conducted for a period of two years in the surface waters of Northern Greece. Samples from four rivers and five lakes were taken seasonally and analyzed for VOCs. The analysis has been performed by purge-and-trap (PAT) gas chromatographic-mass spectrometric (GC-MS) technique. The most commonly encountered VOCs in surface waters were chloroform, carbon tetrachloride, trichloroethylene, dichlorobromomethane, tetrachloroethylene, and chlorodibromomethane.     

Occurrence of glucocorticogenic activity in various surface waters in The Netherlands

Considering the important role that surface waters serve for drinking water production, it is important to know if these resources are under the impact of contaminants. Apart from environmental pollutants such as pesticides, compounds such as (xeno)estrogens have received al lot of research attention and several large monitoring campaigns have been carried out to assess estrogenic contamination in the aquatic environment. The introduction of novel in vitro bioassays enables researchers to study if – and to what extent – water bodies are under the impact of less-studied (synthetic) hormone active compounds. The aim of the present study was to carry out an assessment on the presence and extent of glucocorticogenic activity in Dutch surface waters that serve as sources for drinking water production. The results show glucocorticogenic activity in the range of <LOD – 2.4 ng dexamethasone equivalents L⁻¹ (dex EQs) in four out of eight surface waters. An exploratory time-series study to obtain a more complete picture of the yearly average of fluctuating glucocorticogenic activities at two sample locations demonstrated glucocorticogenic activities ranging between <LOD – 2.7 ng dex EQs L⁻¹. Although immediate human health effects are unlikely, the environmental presence of glucocorticogenic compounds in the ng L⁻¹ range compels further environmental research and assessment.     

Pesticide levels in surface waters in an agricultural-forestry basin in Southern Chile

Residues of five pesticides in surface water were surveyed during 2001 and 2003 in the Traiguen river basin in Southern Chile. Simazine, hexazinone, 2,4-D, picloram herbicides and carbendazim fungicide were selected through a pesticide risk classification index. Six sampling stations along the river were set up based on agricultural and forestry land use. The water sampling was carried out before and after the pesticide application periods and in correspondence to some rain events. Pesticides were analyzed by HPLC with DAD detection in a multiresidue analysis. During 2001, in the first sampling campaign (March), the highest concentrations of pesticides were 3.0 microg l(-1) for simazine and hexazinone and 1.8 microg l(-1) for carbendazim. In the second sampling (September), the highest concentration were 9.7 microg l(-1) for 2,4-D, 0.3 microg l(-1) for picloram and 0.4 microg l(-1) for carbendazim. In the last sampling period (December), samples indicated contamination with carbendazim fungicide at levels of up to 1.2 microg l(-1). In sampling carried out on May 2003, no pesticides were detected. In October 2003, the highest concentrations of pesticides were 4.5 microg l(-1) for carbendazim and 2.9 microg l(-1) for 2,4-D. Data are discussed in function of land use and application periods of the products, showing a clear seasonal pattern pollution in the Traiguen river. Risk assessment for these pesticides was calculated by using a risk quotient (RQ = PNEC/PEC). For picloram the calculated RQ < was 0, which indicates that no adverse effects may occur due to the exposure to this herbicide in the Traiguen river basin. For 2,4-D, simazine, hexazinone, carbendazim RQ > 1, meaning that adverse effects could occur and it is necessary to reduce pesticide exposure in surface waters. It is recommended to continue with a pesticide monitoring program and the implementation of ecotoxicological testing with local and standardized species in order to consider the probability of effects occurrence, with less uncertainty. Thus, it will be more feasible to make some recommendations to regulatory agencies regarding the pesticide use.     

A neural-fuzzy approach to classify the ecological status in surface waters

A methodology based on a hybrid approach that combines fuzzy inference systems and artificial neural networks has been used to classify ecological status in surface waters. This methodology has been proposed to deal efficiently with the non-linearity and highly subjective nature of variables involved in this serious problem. Ecological status has been assessed with biological, hydro-morphological, and physicochemical indicators. A data set collected from 378 sampling sites in the Ebro river basin has been used to train and validate the hybrid model. Up to 97.6% of sampling sites have been correctly classified with neural-fuzzy models. Such performance resulted very competitive when compared with other classification algorithms. With non-parametric classification-regression trees and probabilistic neural networks, the predictive capacities were 90.7% and 97.0%, respectively. The proposed methodology can support decision-makers in evaluation and classification of ecological status, as required by the EU Water Framework Directive.     

Impact of droughts on industrial emissions into surface waters

Environmental Science and Pollution Research - In this paper, we examine the impact of droughts on industrial emissions into surface waters and transfers to publicly owned treatment works (POTWs)....     

慧星试验对水体安全性分析研究

利用彗星试验检测苏南某湖泊湖心区、长江某取水口及其给水处理厂出水水样的遗传毒性,并对结果进行分析研究.结果表明,各水样均能引起DNA损伤,在丰水期致DNA损伤作用的大小顺序为给水厂出水水样＞湖泊水样＞长江取水口水样;在枯水期致DNA损伤作用的大小顺序为湖泊水样＞长江取水口水样＞给水厂出水水样.随着染毒剂量的加大,细胞损伤率增加,细胞受损的程度也在加重,并向3、4级损伤集中,呈明显的剂量-效应关系.     

Chitosan membranes as sorbents for trace elements determination in surface waters

Purpose  

Chitosan membranes (non-crosslinked, crosslinked, and modified with l-cysteine) were evaluated as sorbents prior to electrothermal atomic absorption spectrometry (ETAAS) determination of total dissolved metal content in surface water samples.     

Contamination by selected chlorinated pesticides in surface waters in Hanoi, Vietnam

Fifteen insecticides, which were banned in Vietnam in the period from 1990 to 1998, were chosen for the investigation of surface water samples in Hanoi and its surroundings. The investigation was focused on an area of approximately 30 by 20 km. Thirty water samples, in total were analysed: 11 samples from the Red river, seven from the Duong river, four from various lakes (West lake, Thuyen Quang, Bay Mau, Ba Mau), six from irrigation canals and two samples from wells. The procedure was repeated in November 1998 and in August 1999. The results showed that the contamination of the banned pesticides was highest in the rivers and then in the irrigation canals, followed by the lakes and wells. These pesticides could hardly be determined in just two drinking water samples (wells) and their concentrations rarely exceeded detection limits (0.05-0.25 ng l(-1)). The mean concentrations of sigmaHCHs (alpha, beta, gamma, delta-HCH) and sigmaDDTs (2,4'-, 4,4'-DDE; 2,4'-, 4,4'-DDD; 2,4'-, 4,4'-DDT) in the rivers were 17.2 +/- 71.8 and 43.7 +/- 79.9 ng l(-1) in the dry season (DS, November 1998), 29.3 +/- 117 and 56.1 +/- 65.6 ng l(-1) in the rainy season (RS, August 1999), respectively. However, the highest concentration of DDTs detected in a river sample (DS): 0.324 microg l(-1) was much lower than their allowable limit of concentration in surface waters, which is accorded with Criteria of Vietnam (1995) (DDTs < 10 microg l(-1)). Moreover, endrin, heptachlor, aldrin were also detected in most of water samples with considerable mean concentrations in rivers: 25.3 +/- 40.5, 17.4 +/- 23.8, 11.0 +/- 9.02 ng l(-1) in the DS and 18.5 +/- 23.2, 19.3 +/- 29.0, 12.8 +/- 8.44 ng l(-1) in the RS, respectively. Heptachlor epoxide (isomer A) and dieldrin were detected in some water samples with lowest concentrations.     

Priority volatile organic compounds in surface waters of the southern North Sea

The occurrence of 25 volatile organic compounds (VOCs) was studied from April 1998 to October 2000 in the southern North Sea. Target VOCs were selected from lists of priority pollutants for the marine environment and included, e.g., chlorinated short-chain hydrocarbons (CHCs), monocyclic aromatic hydrocarbons (MAHs), and chlorinated monocyclic aromatic hydrocarbons (CMAHs). Water samples were taken from the Channel, the Belgian Continental Shelf, the mouth of the Scheldt estuary and the Southern Bight, and were analysed by purge-and-trap and high-resolution gas chromatography-mass spectrometry. All data were produced by analyses deemed 'in control' by a rigorous quality assurance/quality control program provided by QUASIMEME (Quality Assurance of Information for Marine Environmental Monitoring in Europe). Chloroform and trichloroethene were commonly detected at concentrations up to 1900 and 270 ng l(-1), respectively. The other CHCs were generally found below 5 ng l(-1), and rarely exceeded 10 ng l(-1). Concentrations of MAHs were at least one order of magnitude higher than those of the CHCs. The higher levels were attributed to anthropogenic emissions from oil-related activities in coastal areas. CMAHs, except chlorobenzene and 1,4-dichlorobenzene, were hardly detected in North Sea waters. The levels of several CHCs and MAHs were shown to decrease compared to previous investigations in 1994-1995, probably as a result of on-going emission reduction efforts. The occurrence of 1,1,1-trichloroethane, for instance, was substantially reduced since the Montreal Protocol was implemented in 1995.