Part I: Temporal and spatial distribution of multiclass pesticide residues in lake waters of Northern Greece: application of an optimized SPE-UPLC-MS/MS pretreatment and analytical method

The present work describes the application of an analytical procedure, utilizing ultra performance liquid chromatography (UPLC) coupled with mass spectrometry instrumentation, for the determination of 253 multiclass pesticides, classified in six different groups. Solid phase extraction was applied for the isolation and pre-concentration of target compounds in water samples. Surface waters of the lakes located in Northern Greece (Volvi, Doirani, and Kerkini), were collected in two time periods (fall/winter 2010 and spring/summer 2011) and analyzed, applying the developed analytical methods. Spatial distribution of detected pesticides was visualized using interpolation methods and geographical information systems (GIS). Pesticides with maximum concentrations were amitrole, propoxur, simazine, chlorpyrifos, carbendazim, triazophos, disulfoton-sulfone, pyridaben, sebuthylazine, terbuthylazine, atrazine, atrazine-desethyl, bensulfuron-methyl, metobromuron, metribuzin, rotenone, pyriproxyfen, and rimsulfuron. In Lake Kerkini, mainly carbamates and triazines were determined at elevated concentrations, near the coastal point of the NW side of the lake. Seasonal variations were strong among the applied pesticide classes and determined concentrations, indicating the contribution of pesticide application patterns and rainfall. Lake Doirani exhibited organophosphate pesticides at higher concentrations mainly at coastal points, while triazines emerged as the main pollutant during spring sampling. Lake Volvi exhibited the highest pesticide concentrations, mostly triazines and ureas at the central part of the lake. The occurrence of extreme values and nonconstant seasonal variations indicated that the concentrations were increased disproportionately during the second sampling, as a result of the varying contribution of pollution sources right after the application period. In all cases, the total concentration of pesticides increased during the second sampling period.     

Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments.

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean-up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean-up for sediment extract was carried out on a 10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL. The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'-DDT and endosulfan sulphate, which was 0.01 mg/kg. The detection limit for organochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 microgram/kg and for organophosphate pesticides less than 10 micrograms/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Occurrence of organophosphorus compounds in polluted marine sediments near a pesticide manufacturing plant

Sediment samples from 23 sampling stations in Nissum Broad (Jutland, Denmark) have been analysed for their contents of 8 organophosphorus compounds: 4 pesticides and 4 related triesters.Only in a few samples, all collected within a short distance from a pesticide manufacturing plant, detectable levels of organophosphates have been observed. The levels ranged from less than 1 μg/kg (ppb) up to 3, 8 mg/kg (ppm) for single compounds.One compound, triethylphosphate, occurred at low concentrations (<1 ppb) in many sediment samples independently of the distance from the chemical plant. Assumably, for this compound, other sources of pollution than the chemical plant may be considered.     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Nutrient dynamics in shallow lakes of northern greece

GOAL, SCOPE, BACKGROUND: Shallow lakes display a number of features that set them apart from the more frequently studied deeper systems. The majority of lakes in Northern Greece are small to moderate in size with a relatively low depth and are considered as sites of high value of the wetland habitat. However, the water quality of these lakes has only been evaluated segmentally and occasionally. OBJECTIVE: The objectives of this study were to thoroughly investigate nitrogen and phosphorus speciation in lakes of a high ecological significance located in N. Greece, in order to evaluate their eutrophication status and possible nutrient limitation factors, and to investigate the main factors/sources that affect the water quality of these systems. METHODS: An extensive survey was carried out during the period from 1998-1999. Water samples were collected on a monthly basis from lakes Koronia, Volvi, Doirani, Mikri Prespa and Megali Prespa located in N. Greece. Water quality parameters (temperature, dissolved oxygen, pH and conductivity), organic indices (COD, BOD5), and N- and P-species (NO3(-), NO2(-), NH4(+), and PO4(3-), Kieldahl nitrogen and acid-hydrolysable phosphorus) were determined according to standard methods for surface water. Statistical treatment of the data was employed. RESULTS AND CONCLUSIONS: The physicochemical parameters determined in the lakes studied revealed a high temporal variation. The trophic state of the lakes ranged from meso- to hypertrophic. The nutrient limiting factor varied among lakes suggesting either P-limitation conditions or mixed conditions changing from P- to N-limitation throughout the year. Urban/industrial activities and agricultural runoff are the major factors affecting all lakes, although with a varying contribution. RECOMMENDATION AND OUTLOOK: This lake-specific research offers valuable information about water quality and nutrient dynamics in lakes of significant ecological value located in N. Greece that can be useful for an effective pollution control/management of these systems. Due to the large intra-annual variability of certain physicochemical parameters, a properly designed monitoring program of lake water is recommended.     

Pesticide residues in river sediments from the Pantanal Wetland, Brazil

Sediment samples from 25 sites in 17 rivers of the Pantanal (Brazil) were analyzed with the objective of evaluating pesticide contamination in sediments. Samples were extracted with an acetone, ethylacetate, and water mixture 2:2:1 (v/v/v). The extract was purified by flash chromatography with aluminum oxide and florisil. A multiresidue gas chromatography-mass spectrometry method was applied to monitor 23 pesticides of different chemical classes (organochlorine, organophosphorus, triazines, anilides and pyrethroids) with some of their degradation products. Compounds identified in sediment samples included lambda -cyhalothrin (1.0 to 5.0 micro g kg(- 1)), p,p'-DDT (3.6 micro g kg(- 1)), deltamethrin (20.0 micro g kg(- 1)) and permethrin (1.0 to 7.0 micro g kg(- 1)).     

Effects of experimental acidification on mobilisation of metals from sediments of limed and non-limed lakes

In order to study the influence of pH on the mobilisation of metals from lake sediments, intact sediment cores with overlying water were sampled from one lime treated lake and one acidified lake. The overlying water of two cores from each lake was successively acidified to pH 4.2 over a period of 3 months. In the acid treated samples from the limed lake, the initial concentrations of Al, Cd, Mn, Pb and Zn in the overlying water were generally lower and the final concentrations were higher than in the acid treated samples from the acidified lake. The labile inorganic fraction of Al (Al(i)) was increasingly dominating as pH decreased. Redox potential and pH in the sediment indicated that the upper two centimetres were involved in the exchange reactions. The experiment showed that mobilisation of metals from sediments can occur and the results indicated that mobilisation could contribute to increased concentrations of metals in lake water during reacidification of formerly lime treated lakes.     

Commercial trials evaluating the novel use of ethyl formate for in-transit fumigation of shipping containers

Sediment samples from 25 sites in 17 rivers of the Pantanal (Brazil) were analyzed with the objective of evaluating pesticide contamination in sediments. Samples were extracted with an acetone, ethylacetate, and water mixture 2:2:1 (v/v/v). The extract was purified by flash chromatography with aluminum oxide and florisil. A multiresidue gas chromatography-mass spectrometry method was applied to monitor 23 pesticides of different chemical classes (organochlorine, organophosphorus, triazines, anilides and pyrethroids) with some of their degradation products. Compounds identified in sediment samples included λ -cyhalothrin (1.0 to 5.0 μ g kg^{? 1}), p,p′-DDT (3.6 μ g kg^{? 1}), deltamethrin (20.0 μ g kg^{? 1}) and permethrin (1.0 to 7.0 μ g kg^{? 1}).     

Persistent organochlorine pesticide residues in fish, sediments and water from Lake Bosomtwi, Ghana

Some organochlorine pesticide residues in tilapia fish (Tilapiazilli), sediment and water samples from Lake Bosomtwi (the largest natural lake in Ghana) were determined to find out the extent of pesticide contamination and accumulation in the lake. The extracted residues were analyzed on a micro-capillary gas chromatograph equipped with electron capture detector. DDE (p,p'-1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene) was the predominant residue in all the samples analyzed; detected in 82% of water samples, 98% of sediment samples and 58% of fish samples at concentrations of 0.061+/-0.03 ng g(-1), 8.342+/-2.96 ng g(-1) and 5.232+/-1.30 ng g(-1), respectively. DDT (p,p'-1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane) was detected in 78% at a mean concentration 0.012+/-0.62 ng g(-1) of water samples analyzed. The mean concentrations of DDT in sediments and fish were 4.41+/-1.54 ng g(-1) and 3.645+/-1.81 ng g(-1), respectively. The detection of lower levels of DDT than its metabolite, DDE, in the samples implies that the presence of these contaminants in the lake is as result of past usage of the pesticides.     

Phosphorus fractionation in lake sediments--lakes Volvi and Koronia, N. Greece

Sediments from two lakes, the meso-to-eutrophic Volvi and the hypertrophic Koronia, located in N. Greece were examined on the basis of P-fractionation. In both lakes, the rank order of P-fractions was HCl-P > NaOH-P > BD-P > NH4Cl-P. The loosely sorbed phosphorus (NH4Cl-P) represented < 1% of the sedimentary inorganic phosphorus, while the reductant phosphorus (BD-P) ranged 5-6%. The calcium bound phosphorus (HCl-P) showed considerable contribution (59-74%) to the sedimentary inorganic P-loads. The metal oxide bound phosphorus (NaOH-P) was higher in the hypertrophic (30-35%) than in the meso-to-eutrophic system (19-28%). Fine-sized sediments exhibited significantly higher concentrations of HCl-P in Volvi and NH4Cl-P in Koronia. Sampling month had significant effect in variance of most P-fractions and other sediment features in both lakes. Use was also made of multivariate statistics to identify the factors which influence the sedimentary phosphorus. NaOH-P was the most reactive fraction in Lake Volvi. Iron compounds and organic matter seem to play a significant role in regulating this labile P-budget. NH4Cl-P was the more reactive fraction in Lake Koronia which was influenced by sedimentation of P-absorbed on clay/silt fine particles.     

Influence of trophic status on PCB distribution in lake sediments and biota

We investigated the relationship between trophic status and polychlorinated biphenyl (PCB) distribution in 19 Swedish lakes. We analyzed PCB in water, phytoplankton, zooplankton, fish and sediment during two sampling periods, in spring and summer. The mass of sigma PCB in the lake sediments was positively related to lake trophy, i.e. more PCBs were accumulated and buried in the sediment of eutrophic lakes than in oligotrophic lakes. In the oligotrophic lakes a greater fraction of the total PCB load was dissolved in water. We conclude that this is a result of higher sedimentation rates in eutrophic lakes and relatively lower turnover of organic carbon in the water column of the shallow, eutrophic lakes. In the stratified lakes, the amount of PCB per cubic meter in the epilimnion decreased from spring to summer. We suggest that sedimentation of plankton beneath the thermocline during stratification act as a sink process of PCBs from the epilimnion.     

Possible alkylation of inorganic Hg(II) by photochemical processes in the environment

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (on-line SPE-LC-ESI-MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L⁻¹, respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L⁻¹, were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.     

Levels of glyphosate in surface waters, sediments and soils associated with direct sowing soybean cultivation in north pampasic region of Argentina

Levels of glyphosate were determined in water, soil and sediment samples from a transgenic soybean cultivation area located near to tributaries streams of the Pergamino-Arrecifes system in the north of the Province of Buenos Aires, Argentina. Field work took into account both the pesticide application and the rains occurring after applications. The pesticide was analysed by HPLC-UV detection, previous derivatization with 9-fluorenylmethylchloroformate (FMOC-Cl). In addition, SoilFug multimedia model was used to analyse the environmental distribution of the pesticides. In the field, levels of glyphosate in waters ranged from 0.10 to 0.70mg/L, while in sediments and soils values were between 0.5 and 5.0mg/Kg. Temporal variation of glyphosate levels depended directly on the time of application and the rain events. The results obtained from the application of the model are in accordance with the values found in the field.     

(汍)汊湖水体和表层沉积物中有机氯农药分布特征

用GC/ECD内标法定量测定了(汍)汉湖水体和表层沉积物中的有机氯农药(OCPs).(汍)汊湖水样和表层沉积物中20种OCPs均有检出.表层沉积物上层中(0～2 cm)的OCPs明显高于下层(2～10 cm),这是(汍)汉湖具有稳定的水动力条件所致.氯丹在表层沉积物中浓度最高,与该化合物在环境中的强稳定性以及在该地区的大量使用有关.表层沉积物样品DCHsO2上层OCPs中o,p'-DDT主要成分,表明近期可能有新的DDTs,特别是含大量o,p'-DDT的三氯杀螨醇的使用.DDD/DDE则显示表层沉积物上层DDTs的降解主要处在厌氧条件下,而下层处在好氧条件下.     

Flux estimates and sedimentation of polychlorinated naphthalenes in the northern part of the Baltic Sea

The concentrations and fluxes of polychlorinated naphthalenes (PCNs) were measured in surface sediments, and settling particulate matter collected in sediment traps, at two coastal and two offshore sampling stations in the Gulf of Bothnia, northern Baltic Sea, Sweden. The PCN concentrations (of tetra- to hepta-chloro congeners) in the surface sediments ranged from 0.27 to 2.8 ng/g dry weight and were of the same order of magnitude as background concentrations reported previously in Europe. The PCN fluxes in the southern basin (0.93 and 0.86 microg/m2/year) of the Gulf of Bothnia were higher than those in the northern basin (0.58 and 0.49 microg/m2/year); they were also higher near the coast than in the open sea. These PCN fluxes are similar to the pre-industrial levels determined from lake sediments in northwest England. The PCN homologue distribution changed from a relatively even distribution in samples collected near the coast, to TeCNs dominating in the samples from the open sea. This indicates that higher chlorinated PCNs are deposited and retained in sediments to a higher degree near the coast. The total annual deposition of PCNs in sediments in the Gulf of Bothnia was estimated to be 91 kg/year.     

Spatial variation of organochlorine pesticides and dissolved organic matter in urban closed lakes

Abstract

Closed lakes located in urban parks act as sinks of organochlorine pesticides (OCPs), which have been used, for decades, as insecticides, herbicides and fungicides. The closed lakes from Bucharest, Romania, are periodically managed to prevent eutrophication and accumulation of pollutants. However, it is not known if these practices reduce or enhance the legacy pollution with OCPs. The aim of this study was to explore the spatial variation of OCPs in closed lakes. The total concentration of OCPs in water and sediments ranged between 0.0176 and 37.1?µg/L, and between 122 to 1,890?ng/g, respectively. The concentrations of OCPs were compared with the consensus-based sediment quality guidelines (SQGs) in order to evaluate the ecological risks of sediments. The highest potential adverse effects were associated with γ-HCH exposure. Periodical draining and dredging of lakes lead to the resuspension of contaminants, increasing pesticide bioavailability and accumulation in sediments. In addition, we observed that fluorescent dissolved organic matter (DOM) might influence the OCPs cycle. The quantity and character of fluorescent DOM can provide further insight into OCPs degradation. Also, this study may help urban planners to determine the state of urban waters and to find the best solution for water management.     

Persistent toxic substances in remote lake and coastal sediments from Svalbard, Norwegian Arctic: Levels, sources and fluxes

Surface sediments from remote lakes and coastal areas from Ny-Ålesund, Svalbard, Norwegian Arctic were analyzed for polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). Relatively high levels of PAHs were encountered from several lakes from Ny-Ålesund, which were within the range of levels reported for European high mountain lakes and some urban/industrialized areas in the world, pointing to the role of remote Arctic lakes as potential reservoir of semi-volatile organic compounds. Specific patterns of PBDEs were observed, showing higher concentrations of lower brominated compounds such as BDE-7, 17 and 28. Estimated surface sediment fluxes of PAHs in Ny-Ålesund remote lakes were similar to those observed for some European high mountain lakes. The current PAH levels in sediments from three lakes exceeded Canadian sediment quality guidelines, suggesting the presence of possible risks for aquatic organisms and the need for further studies.     

Levels and distribution of Dechloranes in sediments of Lake Taihu,China

The occurrence and spatial distribution of dechloranes including mirex, dechlorane plus (DP), dechlorane (Dec) 602, Dec 603, and Dec 604 in surficial sediments of Lake Taihu were investigated in this study. The concentrations of mirex and DP ranged from below detection limit (BDL) to 1.29 ng g^?1 dw and 0.051 to 2.10 ng g^?1 dw, respectively. Dec 602, Dec 603, and Dec 604 on the other hand, were BDL in any of the samples. The contamination levels of DP were higher than that of Mirex at 21 of all 22 sampling sites. Levels of mirex and DP in the lake sediments were correlated when an extremely high mirex value was removed. Both mirex and DP levels were correlated with the amount of organic matters in the sediment samples. Spatial distribution of mirex and DP suggested that these two chemicals in the lake had similar input sources except for one site. Comparison to previously reported flame retardants’ levels in the sediments shows that DP levels were similar with the levels of tetrabromobisphenol A, hexabromocyclododecane but lower than PBDEs and organophosphates levels in Lake Taihu. The higher levels in the north-east part of Lake Taihu adjacent to two major cities: Wuxi and Suzhou, indicated that city effluent might be a major source for DP contamination in the lake.     

Organochlorine and organophosphorus pesticide residues in the Atoya river basin, Chinandega, Nicaragua

The hydrographic basin of the Atoya river, located in the Department of Chinandega, one of the main cotton producing regions in Nicaragua, is intensively contaminated by pesticides. Samples of river waters and sediments, as well as strategically selected wells have been analyzed to study variations in the concentrations of organochlorine and organophosphorus pesticide residues between the dry season (November-April) and the rainy season (May-June). Generally, higher concentrations of pesticides have been detected in the river waters and sediments in the dry season. DDT, DDD, DDE compounds and toxaphene are the most frequent organochlorine residues found in the water and sediment samples, while endrin, aldrin, dieldrin and lindane are mainly found in the waters of rivers and wells. Organophosphorus compounds were rarely detected. However, residues of ethion, methyl-parathion and ethyl-parathion were found in high concentrations in some river and well water samples. Generally, organochlorine compounds tend to accumulate in the fine grain-size fractions, rich in organic matter, except DDE, which concentrates basically in the coarse grain-size fractions.