Fate of herbicide CNP in rivers and agricultural drainages

The occurrence and fate of a herbicide CNP (2,4,6-trichlorophenyl-4′-nitrophenylether) in rivers and agricultural drainages was investigated. CNP residues in water samples were extracted by adsorption on a macroreticular XAD-2 resin column and subjected to gas chromatographic analysis using an electron capture detection after desorption from the column and concentration. The minimum detectable amount was 0.04 ng and a positive identification of CNP residue in water samples was obtained with a combined gas chromatography-mass spectrometry-computer system when 500 ng of CNP was injected. CNP residues were detected in water samples taken in June to September, and these levels were between 0.01 and 16.67 μg l⁻¹. The maximum level was found in a sample taken on 13th July, 1977, about a month after beginning rice seedling transplantation, and the minimum level was detected on August 29th, 1977. However CNP residue levels were increased again in September because flooded water on the paddy fields was excluded. CNP was more persistent in the aquatic environment than a herbicide benthiocarb.     

Gas chromatographic-mass spectrometric identification of phenols and aromatic acids in river waters

The ethyl acetate extracts of water samples from two urban rivers in Tokyo were analyzed for phenols and aromatic acids by using a combined gas chromatograph-mass spectrometer after separating by solvent extraction and silica gel column chromatography. The following phenols and aromatic acids were identified: pentachlorophenol, bisphenol A, phthalic acid, trimesic acid, p-hydroxybenzoic acid, vanillic acid, syringic acid, p-coumaric acid, and ferulic acid. The presence of o- and m-hydroxybenzoic acids were suggested by mass fragmentography. The sources of those compounds are considered.     

Analysis of the antioxidant butylated hydroxytoluene (BHT) in water by means of solid phase extraction combined with GC/MS

The antioxidant 3,5-di-tert-butyl-4-hydroxy-toluene (BHT) is widely used as an additive to increase the tenability of food and plastics. BHT is degraded to 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO) in mammals, as well as in the natural environment such as in water and soils. BHT-CHO has been studied extensively in terms of their potential toxicities. The present investigation was carried out to quantify BHT and BHT-CHO in river, ground, rain and drinking water obtained from several locations in Germany. Apart from the compounds mentioned above, 1,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane (2-BHT), which is a dimer of BHT, was also detected in the extracts of some ground water samples. The applied analytical method is based on solid phase extraction (SPE) to concentrate trace compounds from water samples followed by gas chromatography/mass spectrometry (GC/MS) of the extracts. A total of 51 of the respective water samples were used for extraction purposes and analyte recoveries were all > or = 80%. The determination limit for BHT was 5 ng l(-1) and for BHT-CHO 16 ng l(-1). The standard deviations for the analytical procedure were 6% for BHT and 10% for BHT-CHO. The use of the antioxidant BHT in Germany has resulted in water concentrations of 7-791 ng l(-1) in the rivers Rhine, Elbe, Main, Oder, Nidda and Schwarzbach. The degradation product BHT-CHO was also detected in the river water samples at concentrations between 29 and 223 ng l(-1). The concentrations of BHT measured in German rivers are lower compared to values measured in the USA and Japan 20 years ago. In ground water, levels for BHT varied from non-detectable up to 2156 ng l(-1) and for BHT-CHO from non-detectable up to 674 ng l(-1). Both compounds were also detected in rain water in Frankfurt/Main at a concentration of 1797 ng l(-1) for BHT and 59 ng l(-1) for BHT-CHO.     

Water quality and diatom communities in two catalan rivers (N.E. Spain)

Benthic diatom assemblages have been used to evaluate the water quality of two rivers subjected to marked human influences. These rivers, the Llobregat and the Ter, are located in N.E. Spain, and supply water for industrial, agricultural and urban requirements of roughly three million people. The diatom communities in the headwaters are similar in both rivers (Achnanthes minutissima, Cymbella ventricosa, Gomphonema anguslatum). Species of Navicula, Nitzschia and Gomphonema develop in the middle reaches of both rivers when not disrupted by extraneous factors. In the river Ter significant pollution modifies this community and Nitzschia palea, Nitzschia gandersheimiensis and Gomphonema parvulum appear as the most tolerant species. In the Llobregat, the pollution from the salt mine operations also modifies the diatom assemblage and Nitzschia frustulum, Surirella ovata, Navicula atomus are the most abundant species. Reservoirs in the river Ter improve the quality of water and a community of Fragilaria sp. pl. becomes dominant downstream.     

Identification of potential habitats of gray-faced buzzard in Yatsu landscapes by using digital elevation model and digitized vegetation data

Potential habitats of gray-faced buzzard (Butastur indicus), one of the umbrella species in agro-forested landscape in Japan, were identified in this study based on a precise landscape classification of small valleys called Yatsu, using 50 m-grid digital elevation model and digitized vegetation data. This study mainly consists of two phases: the first is to identify and classify the landscape structure of small valleys, and the second is to identify potential habitats of gray-faced buzzards, one of the umbrella species in this landscape. In the first phase, landscape types around Yatsu valleys in the study area were classified into four types based on the land-use patterns in the cross-sectional direction of valleys. Traditional landscape pattern of rice paddies in the valley floor with wooded slopes are now very scarce at under 10%, over 60% of the valleys in the study area are now without rice paddies in valley floor. Rice paddies on the valley floor and the juxtaposition of paddies and woods are known to be an important habitat for many species based on previous field studies. In the second phase, the characteristics of gray-faced buzzard habitat were identified as follows: (1) narrow valley floor, (2) rich accumulation of edge environments between rice paddies and woods, (3) rich accumulation of landscape pattern with rice paddies in valley floor, and with woods on both slopes in the cross-sectional direction of valleys. Based on the identified characteristics of Yatsu landscape, the potential habitats of the buzzard were identified in the study area.     

Identification of organic sulfur compounds and polycyclic hydrocarbons transferred to shellfish from petroleum suspension by capillary mass chromatography

An attempt was made to determine the organic sulfur compounds, usually contained in crude oil, as a marker of oil pollution in shellfish. Short-necked clam (Tapea Angdala phillipinarum A. et Reeve) were maintained in a controlled laboratory environment and in water with a suspension of crude oil. Capillary column gas chromatography-mass chromatography of short-necked clam extract showed the presence of organic sulfur compounds of alkyl-benzothiophene (from C₁–C₆) and dibenzothiophene and alkyl-dibenzothiophene (C₁–C₄). These organic sulfur compounds are a marker of oil pollution of shellfish. Other organic aromatic compounds, naphthalene, alkyl-naphthalene (C₁–C₃), phenanthrene, alkyl-phenanthrene (C₁–C₃), pyrene and alkyl-pyrene (C₁) in soft body of short-necked clam were transferred from oil suspension to shellfish. The concentration factors of organic sulfur compounds according with lapse of time were determined by gas chromatography with an attached flame ionization detector.     

Organic sulfur compounds and polycyclic hydrocarbons transferred to oyster and mussel from petroleum suspension: Identification by gas chromatography and capillary mass chromatography

An attempt was made to determine the organic sulfur compounds usually contained in crude oil as markers of oil pollution in shellfish. The oyster (Crassostrea gigas) and mussel (Mytilus edulis) were maintained in a controlled laboratory environment and in water with a suspension of crude oil. Capillary column gas chromatography-mass chromatography of extracts showed the presence of organic sulfur compounds of alkyl benzothiophene (C₂C₄), dibenzothiophene and alkyl dibenzothiophene (C₁C₄). Coexistence of polycyclic aromatic hydrocarbons with organic sulfur compounds was found in oyster and mussel. The time courses of concentration ratios of organic sulfur compounds in the oyster and the mussel were determined by gas chromatography connected with flame photometric detector.     

Mycoremediation of chlorpyrifos and lambda-cyhalothrin by two species of filamentous fungi

Chlorpyrifos and lambda-cyhalothrin are two of the most commonly used insecticides in agriculture. Their residues reach water courses, affecting aquatic fauna and subsequently human beings. Aspergillus viridinutans and Penicillium implicatum isolated from water drains at El-Giza and El-Ismailia governorates were grown in potato dextrose broth media supplemented with different concentrations of chlorpyrifos and lambda-cyhalothrin. Samples, taken at 0, 7 and 14 days, were analysed for pesticide residues by gas chromatography. The fungal species showed biodegradation potentials of 2.5, 5 and 20 ppm of chlorpyrifos and lambda-cyhalothrin. Degradation percentage reached 100% after 14 days of incubation of both pesticides (2.5 ppm) individually with the two tested fungal species. The values of degradation rate, besides the weights of dry fungal biomasses ensured that the optimum chlorpyrifosconcentration for A. viridinutans and P. implicatum was 5 ppm, while the optimum lambda-cyhalothrin concentration for A. viridinutanswas 5 ppm and 2.5 ppm for P. implicatum.     

Determination of trialkyl and triaryl phosphates in environmental samples

Analytical methods of trialkyl and triaryl phosphate esters in water and sediment were developed. An environmental survey of them was performed using developed methods. The extract with dichloromethane (water sample) or acetone (sediment sample) was analyzed with a gas chromatograph equipped with a flame photometric detector and a gas chromatograph/mass spectrometer after clean-up through Florisil column. The separation of gas chromatography was good with 2% OV-17 + 2% PZ-179 on Uniport HPS. Recoveries fortified with 0.3–3 μg were 71–98% for water sample and 78–95% for sediment sample. In the environmental survey, tributyl phosphate (5–36 ng l^?1), Tris (3-chloropropyl) phosphate (16–176 ng l^?1), Tris (2-chloroethyl) phosphate (TCEP) (14–347 ng l^?1), Tris (2,3-dichloropropyl) phosphate (CRP) (23–136 ng l^?1), triphenyl phosphate (13–31 ng l^?1), and tricresyl phosphate (67–259 ng l^?1) were detected in river water and seawater, and TCEP (13-28 ng g^?1) and CRP (9–17 ng g^?1) were detected in sediment.     

Proportion of methylmercury to the total amount of mercury in river waters in Canada and Japan

The proportions of methylmercury to the total amount of mercury in water were determined for three rivers and were found to be similar (around 30%). The proportion in sewage effluent water showed a similar value. A pretreatment procedure which can analyze a low concentration of mercury and various species of mercury compounds in natural water is described. The mercury concentration in once mercury-polluted rivers was reduced considerably to near background levels (Ottawa River: 6.6 ng l⁻¹; Suimon River: 26.2 ng l⁻¹).     

Polycyclic aromatic hydrocarbons in storm runoff from urban and coastal South Carolina

Stormwater runoff was collected in urbanized areas of South Carolina to investigate the levels and sources of polycyclic aromatic hydrocarbons (PAHs). Mean concentrations of total PAHs in runoff (sum(PAHs), 14 compounds), determined by gas chromatography-mass spectrometry, were 5590 ng/l in the city of Columbia and 282 ng/l in the coastal community of Murrells Inlet. Lower concentrations were found in estuarine water at Murrells Inlet (mean = 35 ng/l) and at undeveloped North Inlet estuary (13 ng/l). The PAH profiles in Columbia and Murrells Inlet runoff were similar to those of atmospheric particulate matter and unlike those in used crankcase oil. Examination of the aliphatic fraction of Columbia runoff samples by gas chromatography with flame ionization detection showed patterns that were more similar to used crankcase oil than to urban aerosols.     

New standards for the determination of geosmin and methylisoborneol in water by gas chromatography/mass spectrometry

Deuterium labelled geosmin and methylisoborneol (MIB) have been synthesized and evaluated as internal standards in the determination of geosmin and MIB in water by closed loop stripping followed by gas chromatography/mass spectrometry (GC/MS). The labelled standards were compared with chloroalkanes added as internal standards either at the time of sampling or immediately before closed loop stripping. When added at sampling time, the new standards enabled accurate determination of the geosmin and MIB present initially, even when the samples were analysed as much as 3 weeks later. The new standards gave better precision and accuracy than the chloroalkanes and overcame the underestimation of initial analyte concentration which usually results from losses of analyte through adsorption, volatilisation, biodegradation etc. during sample storage. Geosmin had a limit of detection of<0.1ng/l and 1 ng/lwas determined with a coefficient of variation (CV) of 1.2% (n = 5). MIB was determined at 1 ng/l with a CV of 3.5% (n = 5).     

Spatial and temporal distribution of pesticide residues in surface waters in northeastern Greece

A monitoring study of 147 compounds in surface river waters from northeastern Greece near Greek/Bulgarian/Turkish borders was carried out during 1999-2007. Based on agricultural use eight sampling points along the rivers Ardas, Evros and Erythropotamos were set up, covering the distance from the Greek/Bulgarian borders down to the river's discharge (river's delta) in the Greek territory. In total, 88 sampling events were carried out from 1999 to 2007. Pesticides were extracted by solid-phase extraction (SPE) and analyzed by gas chromatography-mass spectrometry (GC-EI-MS) using a multiresidue in-house analytical method including pesticides belonging to different chemical classes. Aquatic risk concerning the detected pesticides was assessed on the basis of the risk quotient (RQ = PEC/PNEC). From the 28 compounds (pesticides, metabolites and caffeine) that were detected in surface waters of northeastern Greece the soil applied pesticides were the most frequently detected. High pesticide concentrations were detected within 2 months of their application. Extreme pesticide concentrations were detected in the beginning of the irrigation season or just after high rainfall events. Generally, low levels of pesticide residues were found in the first sampling point (Greek/Bulgarian borders) of all rivers, however o′,p′ DDT, o′,p′ DDE and γ-HCH were mainly detected in this sampling point regarded as cross-boundary contamination. The most commonly encountered compounds in the river waters were atrazine, DEA, alachlor, trifluralin, prometryne, molinate, carbofuran, carbaryl and diazinon. Increased loading (primary as well as secondary peaks) seemed to be a consequence of application (timing, rate, frequency) and intense rainfall during the application period. Aquatic risk assessment revealed that from the 28 compounds that were constantly detected 12 showed non-acceptable risk when median concentrations were used as PEC and 18 when extreme concentrations were used as PEC values.     

Microbial profile and its changing rates of Lake Burullus,Egypt as wastewater receiving body

Understanding the impacts of seasonal variations on fate and distribution of natural and introduced microbes are important for proper public health, risk assessment and water management of Lake Burullus, Egypt (LB) as water receiving body. The effects of mixing processes on microbial loads in Lake and discharged aquacultural wastewater (AQ) and agricultural drainages (AG) were assessed. Microbiological examinations of discharged waters in this study revealed that total bacterial count (TBC), and total coliform count (TCC) were significantly high at P ≤ 0.05 in aquacultural wastewater than both LB and AG. Total fecal coliform count (TFC) and total fecal streptococcus (TFS) were determined and showed that AG has significantly high at P ≤ 0.05 comparing to both LB and AQ. No seasonal differences in‐between all indictors values of LB, while AG wastewater values were mostly higher than both AQ and LB water samples with declining attitude between sampling points. In case of TBC, TCC and TFC, the microbial loads of lake water were highly affected by receiving water but in case of TSF, the water shows no affects. Contrary, for discharged waters, both show reduction in count that is meaning of dilution processes. As excessive discharge of raw wastewater may present a risk related to high increased rate of TBC and TCC in lake water annually by 27.8 and 33.0% at 500 m points, respectively.     

Illicit drugs, a novel group of environmental contaminants

It is now well established that residues from therapeutic drugs consumed by humans can end up, through the sewage system, in the surface water of populated areas. Given that the global production of major illicit drugs is comparable to that of widely used pharmaceuticals, we tested for the presence of drugs of abuse (cocaine, opioids, amphetamines and cannabis derivatives), some related opioid pharmaceuticals (codeine and methadone) and/or their metabolites in Italian and British surface waters. Having identified residues of all major drugs of abuse in raw and treated urban wastewater, we now measured their levels in several rivers and lakes by a selective multi-residue assay based on liquid chromatography-tandem mass spectrometry. Recoveries in surface water were generally higher than 80%, with overall variability of the method lower than 10%. LODs were generally lower than 0.2 ng/L, and LOQs were lower than 0.6 ng/L, with few exceptions. Many of the tested substances were found in both rivers and lakes, at concentrations ranging from high pg/L to high ng/L, with loads in rivers in the range of tenths to hundreds of grams per day. Our data indicate that residues of drugs of abuse have become widespread surface water contaminants in populated areas. Since most of these residues still have potent pharmacological activities, their presence in the aquatic environment may have potential implications for human health and wildlife.     

Occurrence, distribution and fluxes of benzotriazoles along the German large river basins into the North Sea

Benzotriazole (BT) and tolyltriazole (TT) are high production volume chemicals which are used in various industrial and household applications. In this study, the distribution of benzotriazoles in the estuaries of different rivers of central Europe and in the North Sea was analyzed by solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (HPLC-MS/MS). BT as well as TT was detected in all water samples. The concentrations for total benzotriazoles (BTs) ranged from 1.7 to 40 ng/L in the North Sea in costal areas. Concentrations in rivers are from 200 to 1250 ng/L, respectively. The mass flux of total benzotriazoles from the major rivers of central Europe into the North Sea was calculated to 78 t/a, dominated by the Rhine with an individual flux of 57 t/a of BTs. The analysis of the distribution profile in the North Sea showed that the decrease of the concentration was mostly caused by dilution and that the benzotriazoles are poorly degradable in the North Sea. This paper presents the first report of benzotriazoles in the marine environment.     

Levels of DDT and hexachlorocyclohexane in burbot (Lota lota l.) from Russian Arctic rivers

The concentrations of organochlorine pesticides (OCPs =p,p'DDT, p,p'DDD, p,p'DDE, alpha-HCH and gamma-HCH) were measured in the sediments, water and burbot (whole liver and liver lipids) of eight Russian Arctic rivers near their outflows to the Arctic Ocean between 1988 and 1994. DDT was not detected in any river sediments above the limit of quantification (LOQ) of 2.5 ng g(-1) dry wt. Concentrations of DDD and DDE were only found in three of the river sediments above the LOQ of 0.75 ng g(-1) dry wt. DDT and DDE were present in only North Dvina and Pechora river water above the LOQ of 5 ng l(-1), while DDD was not found in any river above this limit. Both alpha- and gamma-HCH were found in all river sediments except for the Kolyma River at concentrations up to 2.4 and 3.5 ng g(-1) dry wt., respectively. In river water, alpha-HCH was as high as 8.6 ng l(-1) in the Ob River and gamma-HCH as high as 7.6 ng l(-1) in the Pechora River. The concentration of both sigmaDDT and sigmaHCH decreased to LOQ levels by about 1992 in both water and sediments. sigmaDDT (up to 70 ng g(-1) wet wt.) and sigmaHCH (maximum 18 ng g(-1) wet wt.) in burbot livers followed a similar temporal trend as in water and sediments. There is a scarcity of OCP data for Russia, but from what is available, we conclude that: (1) contamination of Russian rivers and burbot by OCPs is less severe in the Arctic than at lower latitudes; (2) contamination of Russian Arctic burbot is comparable to, or lower than, similar OCP contamination measured in burbot and other fish in other countries; and (3) the OCP concentrations in Russian burbot pose a negligible health risk to either humans or wildlife.     

Presence of carbamate pesticides in environmental waters from the northwest of Mexico: determination by liquid chromatography

A study on the presence of carbamate pesticides, namely aldicarb, aldicarb sulfoxide, baygon, benthiocarb, carbofuran, 3-hydroxycarbofuran, carbaryl, desmedipham, methiocarb, methomyl, thiodicarb, oxamyl, and propham was made in ground and surface waters from an agricultural zone of the Yaqui Valley located in northwest Mexico. Trace determinations were made by liquid chromatography (LC) with post-column fluorescence detection (EPA method 531.1) or LC-diode array UV detection coupled on-line to a solid-phase extraction (SPE) system and using a 13 x 4.6 mm i.d. precolumn and a 150 x 4.6 mm i.d. analytical column, both packed with a C18 silica. Results indicated that the level of contamination with methiocarb was 5.4 micrograms/L in a groundwater sample and that for 3-hydroxycarbofuran was 18 micrograms/L in a surface water sample. This study provides the basis for a future monitoring program.     

Determination of phenol in the Bangsai River water of Bangladesh by gas chromatography-mass spectrometry

A simple, sensitive and rapid gas chromatography-mass spectrometry (GC-MS) method is proposed for the analysis of some environmentally important highly toxic phenols in water. The concentration level of phenol was determined in water at the sampling stations of Savar, Dhaka Export Processing Zone (DEPZ) and Bank Colony of the Bangsai River, Bangladesh. Water samples were collected from different depth of the sampling stations. The phenolic compounds were extracted with dichloromethane, which was further preconcentrated by evaporation. Different concentrations of toxic phenol were obtained in the river water at the various sampling stations. The concentration of highly toxic phenol was found in the range of 0.01–0.998 μg L⁻¹. This method could permit the analysis of water for phenol as well as phenolic derivatives with detection limit as low as 100 ng L⁻¹.