A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

Desert Water Harvesting to Benefit Wildlife: A Simple, Cheap, And Durable Sub-Surface Water Harvester for Remote Locations

A sub-surface desert water harvester was constructed in the sagebrush steppe habitat of south-central Idaho, U.S.A. The desert water harvester utilizes a buried micro-catchment and three buried storage tanks to augment water for wildlife during the dry season. In this region, mean annual precipitation (MAP) ranges between about 150–250 mm (6″–10″), 70% of which falls during the cold season, November to May. Mid-summer through early autumn, June through October, is the dry portion of the year. During this period, the sub-surface water harvester provides supplemental water for wildlife for 30–90 days, depending upon the precipitation that year. The desert water harvester is constructed with commonly available, “over the counter” materials. The micro-catchment is made of a square-shaped, 20 mL. “PERMALON” polyethylene pond liner (approximately 22.9 m × 22.9 m = 523 m²) buried at a depth of about 60 cm. A PVC pipe connects the harvester with two storage tanks and a drinking trough. The total capacity of the water harvester is about 4777 L (1262 U.S. gallons) which includes three underground storage tanks, a trough and pipes. The drinking trough is refined with an access ramp for birds and small animals. The technology is simple, cheap, and durable and can be adapted to other uses, e.g. drip irrigation, short-term water for small livestock, poultry farming etc. The desert water harvester can be used to concentrate and collect water from precipitation and run-off in semi-arid and arid regions. Water harvested in such a relatively small area will not impact the ground water table but it should help to grow small areas of crops or vegetables to aid villagers in self-sufficiency.     

Drainage Effects on Stream Nitrate-N and Hydrology in South-Central Minnesota (USA)

Excessive nitrate-N in south-central Minnesota ditches and streams is related to land-use change, and may be contributing to the development of the zone of hypoxia in the Gulf of Mexico. Intensive land-use (agricultural management) has progressively increased as subsurface drainage has improved crop productivity over the past 25 years. We have examined water at varying scales for delta18O and, nitrate-N concentrations. Additionally, analysis of annual peak flows, and channel geomorphic features provided a measure of hydrologic change. Laboratory and field results indicate that agricultural drainage has influenced riverine source waters, concentrations of nitrate-N, channel dimensions and hydrology in the Blue Earth River (BER) Basin. At the mouth of the BER shallow ground water comprises the largest source water component. The highest nitrate-N concentrations in the BER and tributaries typically occurred in May and June and ranged from 7-34 mg L(-1). Peak flows for the 1.01-2-yr recurrence intervals increased by 20-to-206% over the past 25 years. Geomorphic data suggest that small channels (ditches) were entrenched by design, whereas, natural that are disconnected from an accessible riparian corridor. Frequent access to a functioning riparian zone is important for denitrification.     

TPH-contaminated Mexican Refinery Soil: Health Risk Assessment and the First Year of Changes

The soil of a coastal Mexican refinery is quite contaminated, especially by hydrocarbons, with detected concentrations up to 130000 mg kg(-1) as TPHs (total petroleum hydrocarbons). The main sources of contamination are pipelines, valves, and old storage tanks, besides the land disposal of untreated hydrocarbon sediments derived from the cleaning of storage tanks. A health risk assessment (HRA) was carried out in order to measure the risk hazard indexes and clean-up standards for the refinery soil. HRA suggested the following actions to be taken: benzene concentrations must be reduced in eight of the 16 studied refinery zones to 0.0074-0.0078 mg kg(-1). Also, vanadium concentration must be reduced in two zones up to a concentration of 100 mg kg(-1). In only one of all of the studied zones, benzo(a)pyrene concentration must be reduced to 0.1 mg kg(-1). After 1 yr, TPHs showed a diminution of about 52%. Even though TPHs concentrations were variable, during 1999 the average concentrations were as much as 15.5 times the goal concentration. For year 2000, TPHs concentrations were only 7.4-fold the proposed value. For the 1999-2000 period, PAHs (polycyclic aromatic hydrocarbons) concentrations decreased by 82%. Some PAHs with 2, 3, 4, and 5 aromatic rings were removed up to 100% values.     

Effects of Roadway Crossings on Leaf Litter Processing and Invertebrate Assemblages in Small Streams

The effects of the Maine Turnpike (Interstate 95) on leaf litter processing were examined in five first- and second-order coastal plain streams in southern Maine, U.S.A. Invertebrate assemblages and red maple leaf softening and loss rates were compared at 53 stations arrayed upstream and downstream of the turnpike. Litter softening rate was not affected by the roadway. Litter loss rate was significantly faster at downstream stations (-0.0024 degree-day(-1)) than at upstream stations or at stations nearest the roadway, which were not different from each other (-0.0022 degree-day(-1)). Litter softening and loss rates were more strongly related to physical and chemical habitat variables than to shredder assemblage characteristics. Significant among-stream differences were observed in most community structural metrics and in biomass of important shredder taxa, but effects of the roadway were rarely consistent among streams. This is attributed in part to habitat variation, which was greater among streams than within streams. This study suggests that while the presence of the Maine Turnpike may influence stream water quality and habitat structure, the relatively subtle effects of roadway runoff and associated habitat modifications on stream ecosystem processes are masked by within- and among-stream variability in litter processing and leaf pack invertebrate assemblage structure.     

Mobilization of aluminium and deposition on fish gills during sea salt episodes--catchment liming as countermeasure

Episodic events may be critical with respect to aluminium (Al) toxicity in moderately acidified salmon rivers. The present work demonstrates that sea salt episodes enhance the toxicity of Al in acidic rivers. The documented sea salt episode (300 [micro sign]M Cl) mobilized positively charged Al species (0.4 to 1.1 [micro sign]M Al(i)), enhanced the Al accumulation on fish gills (0.9 to 10 [micro sign]mol g(-1) dw) and caused increased stress responses (6 to15 mM blood glucose) in fish. Accumulated Al on gills remained high several days after the episode. The presented results are based on a six-week field study in two tributary rivers on the west coast of Norway. Changes in the river water qualities and Al speciation were followed using in situ fractionation techniques. Al accumulation on gills and stress responses were followed for Atlantic salmon (Salmo salar) kept in tanks continually exposed to the changing water quality. The potential mobilization of Al from the two catchments was studied by extracting soils with diluted seawater (salinity of 3). To counteract Al toxicity, one of the tributary catchments has been limed. The potential mobility of Al by sea salt was lower in limed soils compared to acid soils, and the Al deposition on fish gills (<3.5 [micro sign]mol g(-1) dw) and associated stress responses stayed low during the sea salt episode in the river draining the limed catchment. Thus, for acid river systems in coastal areas, catchment liming should be considered as a useful countermeasure for Al toxicity.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Organophosphate flame retardants and plasticisers in wastewater treatment plants

Previous studies have revealed that chlorinated and non-chlorinated organophosphorous flame retardants and plasticisers are important contaminants in German surface waters and it has been demonstrated that wastewater treatment plants contribute to the emission of these substances. In this study temporal development as well as elimination efficiency were determined in two wastewater treatment plants (STP) in the Ruhr/Rhine area at different stages of the wastewater treatment process. The samples were analysed for the non-chlorinated organophosphate esters tri-n-butylphosphate (TnBP), tri-iso-butylphosphate (TiBP), tris-(butoxyethyl)-phosphate (TBEP) and triphenylphosphate (TPP) and the chlorinated organophosphate esters tris-(2-chloro, 1-methylethyl)-phosphate (TCPP), tris-(2-chloro-, 1-chloromethylethyl)-phosphate (TDCP) and tris-(2-chloroethyl)-phosphate (TCEP). The study showed that there were significant differences in the elimination of chlorinated and non-chlorinated organophosphorous flame retardants. The elimination rates ranged from 57-86% for TiBP, TnBP and TBEP at both STP's. No elimination of the chlorinated flame retardants TCPP, TDCP and TCEP was observed in any of the sampled STPs. At both STPs the first treatment steps and the final filtration did not contribute to the elimination of the non-chlorinated organophosphorous flame retardants while the aeration step did. At both STPs the efficiency of the cleaning process concerning the flame retardants was comparable. Thus the type of construction of the STP was not relevant for the elimination of these substances. Additionally a strong day-to-day variation was observed, while in one STP a temporal trend for TCPP during the week was found.     

Natural mercury enrichment in a minerogenic fen--evaluation of sources and processes

Mercury (Hg) records in natural archives such as peat bogs are often used to evaluate anthropogenic or climatic influences on atmospheric Hg deposition. In this context, there is an ongoing discussion about natural sources or processes of Hg enrichment in natural archives. In the present study we estimated Hg fluxes from rock weathering, direct atmospheric deposition and from indirect atmospheric deposition in the catchment of a pristine minerogenic fen (GC2) located in the Magellanic Moorlands, southernmost Chile. The Hg record in the bog covers 11 174 cal. (14)C years and shows Hg concentrations of up to 570 [micro sign]g kg(-1) with an average of 268 [micro sign]g kg(-1). Hg was found to be enriched in the peat by a factor of 81 if compared to the mean Hg concentrations in the rocks of the catchment (3.2 [micro sign]g kg(-1)). Hg and also Pb, Fe, and As were found to be enriched predominately in goethite layers indicating high retention of these elements in the bog by iron oxyhydrates. It could also be demonstrated that the high peat decomposition rates in minerogenic bogs can increase the Hg concentrations in the minerogenic peat by a factor of approximately 2 at the same atmospheric Hg deposition rate if compared to ombrotrophic sites. This study has shown that Hg in minerogenic peat can be naturally enriched especially through the retention by autochthonous formed goethite and can be a solely internal process which does not require increased external Hg fluxes.