Organic carbon effects on aerobic polychlorinated biphenyl removal and bacterial community composition in soils and sediments

Certain organic compounds, including biphenyl and salicylic acid, stimulate polychlorinated biphenyl (PCB) degradation by microorganisms in some environments. However, the usefulness of these amendments for improving PCB removal by microorganisms from diverse habitats has not been extensively explored. This study evaluated the effects of biphenyl, salicylic acid, and glucose on changes in aerobic PCB removal and bacterial communities from an agricultural soil, a wetland peat soil, a river sediment, and a mixture of these samples. PCB removal patterns were significantly different between soils and sediments amended with carbon compounds: (i) terrestrial soil microorganisms removed more PCBs than river sediment microorganisms, particularly with regard to PCBs with >4 chlorine substituents, (ii) glucose-supplemented, agricultural soil microorganisms removed more hexachlorobiphenyl than unsupplemented samples, (iii) biphenyl-supplemented, river sediment microorganisms removed more di- and tri-chlorobiphenyls than unamended samples. Carbon amendments also caused unique shifts in soil and sediment bacterial communities, as determined by specific changes in bacterial 16S rRNA denaturing gradient gel electrophoresis banding patterns. These results indicate that organic carbon amendments had site-specific effects on bacterial populations and PCB removal. Further work is needed to more accurately characterize PCB degrading communities and functional gene expression in diverse types of environments to better understand how they respond to bioremediation treatments.     

Seed treatments containing neonicotinoids and fungicides reduce aquatic insect richness and abundance in midwestern USA–managed floodplain wetlands

Agrochemicals including neonicotinoid insecticides and fungicides are frequently applied as seed treatments on corn, soybeans, and other common row crops. Crops grown from pesticide-treated seed are often directly planted in managed floodplain wetlands and used as a soil disturbance or food resource for wildlife. We quantified invertebrate communities within mid-latitude floodplain wetlands and assessed their response to use of pesticide-treated seeds within the floodplain. We collected and tested aqueous and sediment samples for pesticides in addition to sampling aquatic invertebrates from 22 paired wetlands. Samples were collected twice in 2016 (spring [pre-water level drawdown] and autumn [post-water level flood-up]) followed by a third sampling period (spring 2017). Meanwhile, during the summer of 2016, a portion of study wetlands were planted with either pesticide-treated or untreated corn seed. Neonicotinoid toxic equivalencies (NI-EQs) for sediment (X??=?0.58 μg/kg), water (X??=?0.02 μg/L), and sediment fungicide concentrations (X??=?0.10 μg/kg) were used to assess potential effects on wetland invertebrates. An overall decrease in aquatic insect richness and abundance was associated with greater NI-EQs in wetland water and sediments, as well as with sediment fungicide concentration. Post-treatment, treated wetlands displayed a decrease in insect taxa-richness and abundance before recovering by the spring of 2017. Information on timing and magnitude of aquatic insect declines will be useful when considering the use of seed treatments for wildlife management. More broadly, this study brings attention to how agriculture is used in wetland management and conservation planning.

     

The toxicity and concentrations of PAHs in creosote-contaminated lake sediment

Sediment samples, divided into three layers (0-10, 10-20 and 20-30 cm), were collected from 16 sites in Lake J?ms?nvesi, Central Finland. The acute toxicity of pore waters and elutriates (sediment + water 1:4 v/v) were studied by bioluminescence inhibition test and by immobilisation of water fleas (Daphnia magna Straus). Concentrations of polycyclic aromatic hydrocarbons (PAHs) in sediments and elutriates were measured by gas chromatography using flame ionization detection (GC/FID). The highest total PAH concentration was 3.3 mg/g dry weight in the sediment and up to 1.7 mg/l in the elutriate of the uppermost (0-10 cm) layer, also being the most toxic to photoluminencent bacteria and water flea. When sediment and water mix, like during dredging operations, toxic compounds may spread from the sediment to the water column and can pose on environmental risk.     

Dissipation of glyphosate and aminomethylphosphonic acid in water and sediment of two Canadian prairie wetlands

Glyphosate [N-(phosphonomethyl)glycine] is the active ingredient of several herbicide products first registered for use in 1974 under the tradename Roundup. The use of glyphosate-based herbicides has increased dramatically over the last two decades particularly in association with the adoption of glyphosate-tolerant crops. Glyphosate has been detected in a range of surface waters but this is the first study to monitor its fate in prairie wetlands situated in agricultural fields. An ephemeral wetland (E) and a semi-permanent wetland (SP) were each divided into halves using a polyvinyl curtain. One half of each wetland was fortified with glyphosate with the added mass simulating an accidental direct overspray. Glyphosate dissipated rapidly in the water column of the two prairie wetlands studied (DT₅₀ values of 1.3 and 4.8 d) which may effectively reduce the impact of exposure of aquatic biota to the herbicide. Degradation of glyphosate to its major metabolite aminomethylphosphonic acid (AMPA) and sorption of the herbicide to bottom sediment were more important pathways for the dissipation of glyphosate from the water column than movement of the herbicide with infiltrating water. Presently, we are not aware of any Canadian guidelines for glyphosate residues in sediment of aquatic ecosystems. Since a substantial portion of glyphosate entering prairie wetlands will become associated with bottom sediments, particularly in ephemeral wetlands, guidelines would need to be developed to assess the protection of organisms that spend all or part of their lifecycle in sediment.     

Impact of soil movement on carbon sequestration in agricultural ecosystems

Recent modeling studies indicate that soil erosion and terrestrial sedimentation may establish ecosystem disequilibria that promote carbon (C) sequestration within the biosphere. Movement of upland eroded soil into wetland systems with high net primary productivity may represent the greatest increase in storage capacity potential for C sequestration. The capacity of wetland systems to capture sediments and build up areas of deposition has been documented as well as the ability of these ecosystems to store substantial amounts of C. The purpose of our work was to assess rates of sediment deposition and C storage in a wetland site adjacent to a small first-order stream that drains an agricultural area. The soils of the wetland site consist of a histosol buried by sediments from the agricultural area. Samples of deposited sediments in the riparian zone were collected in 5 cm increments and the concentration of 137Cs was used to determine the 1964 and 1954 deposition layers. Agricultural activity in the watershed has caused increased sediment deposition to the wetland. The recent upland sediment is highly enriched in organic matter indicating that large amounts of organic C have been sequestered within this zone of sediment deposition. Rates of sequestration are much higher than rates that have occurred over the pre-modern history of the wetland. These data indicate the increased sedimentation rates in the wetland ecosystem are associated with increased C sequestration rates.     

Bacterial community structure analyses to assess pollution of water and sediments in the Lake Shkodra/Skadar, Balkan Peninsula

- Goal, Scope, Background. Lake Skadar is the largest lake in Balkan Peninsula, located on the Montenegro-Albanian border. The unique features of the lake and wide range of endemic and rare or endangered plant and animal species resulted in the classification of the Skadar as a wetland site of international significance. In spite of its importance the Lake is influenced by inflowing waters from river Morača and other regional rivers contaminated by the industry, municipal and agricultural activities in the area. Therefore, the Lake has been subject of various physical, chemical, biological and toxicological examinations. However, community-level analyses are most relevant to assess the effect of stressors on aquatic ecosystems. In the present study bacterial community structure among differently polluted sites of the lake was compared by genetic fingerprinting technique. Methods Water and sediment samples were collected from five differently polluted sampling sites on the Lake Skadar in spring and autumn of the same year. The bacterial community structure in the samples was characterized and compared by temporal temperature gel electrophoresis (TTGE) analysis of polymerase chain reaction-amplified bacterial 16S rRNA genes. Results and Discussion The TTGE analysis resulted in many distinguishable and reproducible band patterns, allowing reliable comparison of bacterial communities among sampling sites. Results on the bacterial community structure revealed that three of the selected locations can be considered as sites that have not shown any pollution degradation determined by our method, due to similar structure of bacterial community in the sediment samples. On the other hand, significant shifts in bacterial community structure in the mouth of the river Morača and Plavnica were shown. Since the results coincide with some of the bioassays and chemical analysis performed previously, the changes in bacterial community structure are explained as an effect of antropogenic pollution on the lake ecosystem by waters of river Morača and stream Plavnica. Conclusion The TTGE has proven to be an efficient and reliable method to monitor bacterial dynamics and community shifts in aquatic environment, especially in the sediments. Within the variety of environmental quality assessments the use of TTGE analyses of bacterial community is strongly recommended, particularly as an initial investigation. However, in any conclusion on the state of the environment, the TTGE results should be combined to some other biological, chemical and hydrological data. Recommendation and Outlook Since prokaryotes are a crucial group of organisms in the biosphere, the ecosystem function studies are largely based on bacterial communities. Therefore, bacterial community structure analysis should be a part of an integrated weight of evidence approach in pollution assessment. In case of Triad approach, consisting of chemical analyses, bioassays, and community studies in the field, the TTGE bacterial community structure analyses should be placed in the later Triad leg. In comparison to other community studies, based on various biotic indices, the TTGE bacterial community analysis has proven to be very sensitive, reliable and less time consuming.     

A multiple testing approach for hazard evaluation of complex mixtures in the aquatic environment: the use of diesel oil as a model

Traditional single species toxicity tests and multiple component laboratory-scaled microcosm assays were combined to assess the toxicological hazard of diesel oil, a model complex mixture, to a model aquatic environment. The immediate impact of diesel oil dosed on a freshwater community was studied in a model pond microcosm over 14 days: a 7-day dosage and a 7-day recovery period. A multicomponent laboratory microcosm was designed to monitor the biological effects of diesel oil (1.0 mg litre(-1)) on four components: water, sediment (soil + microbiota), plants (aquatic macrophytes and algae), and animals (zooplanktonic and zoobenthic invertebrates). To determine the sensitivity of each part of the community to diesel oil contamination and how this model community recovered when the oil dissipated, limnological, toxicological, and microbiological variables were considered. Our model revealed these significant occurrences during the spill period: first, a community production and respiration perturbation, characterized in the water column by a decrease in dissolved oxygen and redox potential and a concomitant increase in alkalinity and conductivity; second, marked changes in microbiota of sediments that included bacterial heterotrophic dominance and a high heterotrophic index (0.6), increased bacterial productivity, and the marked increases in numbers of saprophytic bacteria (10 x) and bacterial oil degraders (1000 x); and third, column water acutely toxic (100% mortality) to two model taxa: Selenastrum capricornutum and Daphnia magna. Following the simulated clean-up procedure to remove the oil slick, the recovery period of this freshwater microcosm was characterized by a return to control values. This experimental design emphasized monitoring toxicological responses in aquatic microcosm; hence, we proposed the term 'toxicosm' to describe this approach to aquatic toxicological hazard evaluation. The toxicosm as a valuable toxicological tool for screening aquatic contaminants was demonstrated using diesel oil as a model complex mixture.     

From wetland to farm and back again: phosphorus dynamics of a proposed restoration project

We studied the phosphorus dynamics in a former wetland, which had been converted to a celery farm, and now consists of two shallow, flooded ponds that are being proposed for aquatic habitat restoration. However, like many agricultural areas, this site is plagued by phosphorus legacy issues. Proposed restoration includes hydrologic reconnection of these ponds to its adjacent stream, which are now isolated from one another by an earthen berm, to create a wetland complex. One of the two flooded ponds was partially dredged, whereas the other one has remained undredged. Water column, sediment pore water, and sediment total phosphorus concentrations were significantly greater in the undredged pond compared to the dredged pond, but in both cases phosphorus levels in the water columns (mean TP 929 vs. 133 μg/L in undredged vs. dredged ponds, respectively) would exacerbate downstream water quality issues if hydrologic reconnection occurred without first addressing the phosphorus issue. Sediment isotherm and maximum sorption data indicated that the sediments are close to phosphorus saturation in the undredged pond; simulated dredging of the cores revealed that exposure of deeper sediment layers would increase sorption capacity. Pore water SRP concentrations increased with sediment depth and were significantly greater in the undredged vs. dredged pond at both the 1–4-cm depth (2249 vs. 112 μg/L) and 14–17-cm depth (5506 vs. 222 μg/L). This study provides a framework for other projects that need to balance the competing demands of habitat restoration vs. water quality when restoring wetlands that have been converted to agricultural production.

     

Mitigation of two pyrethroid insecticides in a Mississippi Delta constructed wetland

Constructed wetlands are a suggested best management practice to help mitigate agricultural runoff before entering receiving aquatic ecosystems. A constructed wetland system (180 m × 30 m), comprising a sediment retention basin and two treatment cells, was used to determine the fate and transport of simulated runoff containing the pyrethroid insecticides lambda-cyhalothrin and cyfluthrin, as well as suspended sediment. Wetland water, sediment, and plant samples were collected spatially and temporally over 55 d. Results showed 49 and 76% of the study's measured lambda-cyhalothrin and cyfluthrin masses were associated with vegetation, respectively. Based on conservative effects concentrations for invertebrates and regression analyses of maximum observed wetland aqueous concentrations, a wetland length of 215 m × 30 m width would be required to adequately mitigate 1% pesticide runoff from a 14 ha contributing area. Results of this experiment can be used to model future design specifications for constructed wetland mitigation of pyrethroid insecticides.     

Influence of plants on the reduction of hexavalent chromium in wetland sediments

This work addresses the effect that plants (Typha latifolia and Carex lurida) have on the reduction of Cr(VI) in wetland sediments. Experiments were carried out using tubular microcosms, where chemical species were monitored along the longitudinal flow axis. Cr(VI) removal was enhanced by the presence of plants. This is explained by a decrease in the redox potential promoted by organic root exudates released by plants. Under these conditions sulfate reduction is enhanced, increasing the concentration of sulfide species in the sediment pore water, which reduce Cr(VI). Evapotranspiration induced by plants also contributed to enhance the reduction of Cr(VI) by concentrating all chemical species in the sediment pore water. Both exudates release and evapotranspiration have a diurnal component that affects Cr(VI) reduction. Concentration profiles were fitted to a kinetic model linking sulfide and Cr(VI) concentrations corrected for evapotranspiration. This expression captures both the longitudinal as well as the diurnal Cr(VI) concentration profiles.     

Content, distribution and fate of 33 elements in sediments of rivers receiving wastewater in Hanoi, Vietnam

Untreated industrial and domestic wastewater from Hanoi city is discharged into rivers that supply water for various agricultural and aqua-cultural food production systems. The aim of this study was to assess the content, distribution and fate of 33 elements in the sediment and pore water of the main wastewater receiving rivers. The sediment was polluted with potentially toxic elements (PTEs) with maximum concentrations of 73 As, 427 Cd, 281 Cr, 240 Cu, 218 Ni, 363 Pb, 12.5 Sb and 1240 Zn mg kg(-1) d.w. Observed distribution coefficients (log(10) K(d,obs)) were calculated as the ratio between sediment (mg kg(-1) d.w.) and pore water (mg L(-1)) concentrations. Maxima log(10) K(d,obs) were >4.26 Cd, >6.60 Cu, 4.78 Ni, 7.01 Pb and 6.62 Zn. The high values show a strong PTE retention and indicate the importance of both sorption and precipitation as retention mechanisms. Sulphide precipitation was a likely mechanism due to highly reduced conditions.     

Evaluating the exchange of DDTs between sediment and water in a major lake in North China

A large-scale sampling program was conducted to simultaneously collect surface water, overlying water, pore water, and sediment samples at monthly intervals between March and December 2010 from Baiyangdian Lake, North China to assess the distribution of DDTs and determine the net direction of sediment–water exchange. Total DDT concentrations ranged 2.36–22.4 ng/L, 0.72–21.9 ng/L, 2.25–33.7 ng/L, and 4.42–7.29 ng/g in surface water, overlying water, pore water, and sediments, respectively, which were at the intermediate levels compared to those of other area around the world. Seasonal variations of DDTs were featured by higher concentration in summer. This was likely associated with (a) the increase of land runoff in the summer and (b) application of dicofol and DDT-containing antifouling paints for ships in summer. Sediment–water fugacity ratios of the DDT isomers were used to predict the direction of the sediment–water exchange of these isomers. The sediment–surface water, sediment–overlying water, and sediment–pore water fugacity ratios of DDT isomers averaged 0.34, 0.44, and 0.1, which are significantly lower than the equilibrium status (1.0), suggesting that the net flux direction were from the water to sediment and the sediment acted as a sink for the DDTs. The difference of DDT concentrations between sediment and water samples was found to be an important factor affecting the diffusion of DDT from the water to sediment.     

Responses of Hyalella azteca and phytoplankton to a simulated agricultural runoff event in a managed backwater wetland

We assessed the aqueous toxicity mitigation capacity of a hydrologically managed floodplain wetland following a synthetic runoff event amended with a mixture of sediments, nutrients (nitrogen and phosphorus), and pesticides (atrazine, S-metolachlor, and permethrin) using 48-h Hyalella azteca survival and phytoplankton pigment, chlorophyll a. The runoff event simulated a 1 h, 1.27 cm rainfall event from a 16 ha agricultural field. Water (1 L) was collected every 30 min within the first 4 h, every 4 h until 48 h, and on days 5, 7, 14, 21, and 28 post-amendment at distances of 0, 10, 40, 300 and 500 m from the amendment point for chlorophyll a, suspended sediment, nutrient, and pesticide analyses. H. azteca 48-h laboratory survival was assessed in water collected at each site at 0, 4, 24, 48 h, 5 d and 7 d. Greatest sediment, nutrient, and pesticide concentrations occurred within 3 h of amendment at 0 m, 10 m, 40 m, and 300 m downstream. Sediments and nutrients showed little variation at 500 m whereas pesticides peaked within 48 h but at <15% of upstream peak concentrations. After 28 d, all mixture components were near or below pre-amendment concentrations. H. azteca survival significantly decreased within 48 h of amendment up to 300 m in association with permethrin concentrations. Chlorophyll a decreased within the first 24 h of amendment up to 40 m primarily in conjunction with herbicide concentrations. Variations in chlorophyll a at 300 and 500 m were associated with nutrients. Managed floodplain wetlands can rapidly and effectively trap and process agricultural runoff during moderate rainfall events, mitigating impacts to aquatic invertebrates and algae in receiving aquatic systems.     

Mitigation of chlorpyrifos runoff using constructed wetlands

Constructed wetlands have been proposed as a potential best management practice (BMP) to mitigate effects of pesticide-associated agricultural runoff. Wetland mesocosms (14 m x 59-73 m) were amended with chlorpyrifos to simulate a storm runoff event at concentrations of 73, 147 and 733 microg/l. Water, sediment and plant samples collected weekly for 12 weeks indicated that chlorpyrifos rapidly sorbed to sediment and plant material, with approximately 47-65% of measured chlorpyrifos mass retained within the first 30-36 m of wetland mesocosms. Of the measured mass, approximately 55% and 25% were retained by sediments and plants, respectively. A field-scale evaluation of a constructed wetland's mitigation capability was performed in the Lourens River watershed of Cape Town, South Africa. Results indicate that the wetland was able to retain and considerably decrease the concentration (and hence toxicity) of chlorpyrifos and suspended sediment entering the receiving waterbody (Lourens River). This research provides fundamental answers concerning constructed wetland capabilities that are necessary for constructing field-scale systems within agricultural watersheds.     

Dissipation of glyphosate and aminomethylphosphonic acid in water and sediment of two Canadian prairie wetlands

Glyphosate [N-(phosphonomethyl)glycine] is the active ingredient of several herbicide products first registered for use in 1974 under the tradename Roundup. The use of glyphosate-based herbicides has increased dramatically over the last two decades particularly in association with the adoption of glyphosate-tolerant crops. Glyphosate has been detected in a range of surface waters but this is the first study to monitor its fate in prairie wetlands situated in agricultural fields. An ephemeral wetland (E) and a semi-permanent wetland (SP) were each divided into halves using a polyvinyl curtain. One half of each wetland was fortified with glyphosate with the added mass simulating an accidental direct overspray. Glyphosate dissipated rapidly in the water column of the two prairie wetlands studied (DT(50) values of 1.3 and 4.8 d) which may effectively reduce the impact of exposure of aquatic biota to the herbicide. Degradation of glyphosate to its major metabolite aminomethylphosphonic acid (AMPA) and sorption of the herbicide to bottom sediment were more important pathways for the dissipation of glyphosate from the water column than movement of the herbicide with infiltrating water. Presently, we are not aware of any Canadian guidelines for glyphosate residues in sediment of aquatic ecosystems. Since a substantial portion of glyphosate entering prairie wetlands will become associated with bottom sediments, particularly in ephemeral wetlands, guidelines would need to be developed to assess the protection of organisms that spend all or part of their lifecycle in sediment.     

Characterisation of potentially genotoxic compounds in sediments collected from United Kingdom estuaries

The mutagenic activity bioassay Mutatox was used to assess the mutagenic activity associated with sediments collected from five UK estuaries. Assays were performed on extracts of sediment pore water and residual particulate material isolated from sediment samples collected from the rivers Tyne, Tees, Mersey, and Thames as well as Southampton Water. No mutagenic activity was associated with the pore water extracts, however, 7 of the 28 organic solvent extracts of sediment particulate material contained potential genotoxins. By using Mutatox in association with bioassay-directed fractionation, attempts were made to identify the mutagenic compounds present in the extracts. The fractionation procedure used normal phase solid phase extraction, C18 reverse phase HPLC and cyano/amino bonded silica normal phase HPLC. GC-MS (EI and NICI) analysis was used to identify polycyclic aromatic hydrocarbons (PAH), alkyl substituted PAH, nitro-polycyclic aromatic compounds (nitro-PACs), polycyclic aromatic ketones, oxygenated-PACs, and other known mutagens contributing to the genotoxicity measured in the samples. Some potentially genotoxic compounds remain unidentified.     

Influence of vegetation in mitigation of methyl parathion runoff

A pesticide runoff event was simulated on two 10 m x 50 m constructed wetlands (one non-vegetated, one vegetated) to evaluate the fate of methyl parathion (MeP) (Penncap-M). Water, sediment, and plant samples were collected at five sites downstream of the inflow for 120 d. Semi-permeable membrane devices (SPMDs) were deployed at each wetland outflow to determine exiting pesticide load. MeP was detected in water at all locations of the non-vegetated wetland (50 m), 30 min post-exposure. MeP was detected 20 m from the vegetated wetland inflow 30 min post-exposure, while after 10d it was detected only at 10 m. MeP was measured only in SPMDs deployed in non-vegetated wetland cells, suggesting detectable levels were not present near the vegetated wetland outflow. Furthermore, mass balance calculations indicated vegetated wetlands were more effective in reducing aqueous loadings of MeP introduced into the wetland systems. This demonstrates the importance of vegetation as sorption sites for pesticides in constructed wetlands.     

Evaluating toxicity of Asana XL (esfenvalerate) amendments in agricultural ditch mesocosms

Agricultural ditches primarily serve to remove and store excess water associated with irrigation and storm events. The ability of these ecosystems to mitigate potential contaminants is not well understood. Five sites along a 650-m agricultural ditch located in the Mississippi Delta Management Systems Evaluation Area (MDMSEA) were used to measure fate and effects of an esfenvalerate (insecticide) exposure. Following a 0.64-cm simulated storm event, samples were collected from water and sediments and analyzed spatially from five sites and temporally from 0.5 h to 56 d. Results of aqueous toxicity bioassays indicated that lethality progressed downstream throughout all sampling intervals, while sediment toxicity bioassays only elicited biological responses at the point of pesticide application to the ditch (0 m). Significant reductions in survival of Ceriodaphnia dubia and Pimephales promelas in water were measured at the 0-, 20-, and 80-m sites following application. Ten-day solid phase sediment testing of Chironomus tentans indicated persistent toxicity only at the point of application (0 m) and throughout 56 d (mean=14.4% survival). No lethality or significant reduction in midge growth was measured for remaining downstream sites. These measurements were used to evaluate the potential of agricultural ditches to reduce potential deleterious effects of contaminants in agricultural drainage systems that precede receiving streams.     

Mercury cycling in surface water, pore water and sediments of Mugu Lagoon, CA, USA

Mugu Lagoon is an estuary in southern California, listed as impaired for mercury. In 2005, we examined mercury cycling at ten sites within at most four habitats. In surface water (unfiltered and filtered) and pore water, the concentration of total mercury was correlated with methylmercury levels (R2=0.29, 0.26, 0.27, respectively, p<0.05), in contrast to sediments, where organic matter and reduced iron levels were most correlated with methylmercury content (R2=0.37, 0.26, respectively, p<0.05). Interestingly, levels for percent methylmercury of total mercury in sediments were higher than typical values for estuarine sediments (average 5.4%, range 0.024-38%, n=59), while pore water methylmercury Kd values were also high (average 3.1, range 2.0-4.2l kg(-1), n=39), and the estimated methylmercury flux from sediments was low (average 1.7, range 0.14-5.3ng m(-2) day(-1), n=19). Mercury levels in predatory fish tissue at Mugu are >0.3ppm, suggesting biogeochemical controls on methylmercury mobility do not completely mitigate methylmercury uptake through the food web.     

Trace level determination of selected sulfonylurea herbicides in wetland sediment by liquid chromatography electrospray tandem mass spectrometry

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg^{? 1}. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg^{? 1}). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg^{? 1}.