Use of pharmaceuticals and pesticides to constrain nutrient sources in coastal groundwater of northwestern Long Island, New York, USA

In developed, non-agricultural, unsewered areas, septic systems and fertilizer application to lawns and gardens represent two major sources of nitrogen to coastal groundwater, in addition to atmospheric input. This study was designed to distinguish between these two possible nitrogen sources by analyzing groundwater samples for pharmaceutical residuals, because fertilizers do not contain any of these pharmaceuticals, but domestic wastewater commonly does. In addition, several herbicides and insecticides used in lawn treatment were analyzed as indicators of nitrogen delivery to groundwater from fertilizers. Groundwater samples were taken through piezometres at shoreline sites in unsewered areas surrounding Northport Harbor and in sewered areas adjacent to Manhasset Bay (hereafter referred to as "Northport" and "Manhasset", respectively), both in northwestern Long Island, USA. Excessive nitrogen loading has led to reduced dissolved oxygen concentrations in Long Island Sound, and the groundwater contribution to the nitrogen budget is poorly constrained. The frequent detection of the anticonvulsant compound carbamazepine in groundwater samples of the Northport Harbor area (unsewered), together with the fact that few pesticides associated with lawn applications were detected, suggests that wastewater input and atmospheric input are the likely sources of nitrogen in the Northport groundwater. High concentrations of nitrogen were also detected in the Manhasset (sewered) groundwater. The low detection frequency and concentration of carbamazepine, however, suggest that the sewer system effectively intercepts nitrogen from wastewater there. The likely sources of nitrogen in the Manhasset groundwater are atmospheric deposition and lawn fertilizers, as this area is densely populated.     

In situ polar organic chemical integrative sampling (POCIS) of steroidal estrogens in sewage treatment works discharge and river water

A passive sampler (the polar organic chemical integrative sampler; POCIS) was assessed for its ability to sample natural estrogens (17β-estradiol, E2; estrone, E1 and estriol, E3) and the synthetic estrogen (17α-ethynylestradiol, EE2) in the outlet of a sewage treatment works over several weeks. The performance of the POCIS was investigated and optimised in the laboratory before field deployment with high recoveries (66-99%) were achieved for all estrogens. Moreover, it was shown that POCIS does not exhibit any preferential selectivity towards any of the target compounds. The sampling rates of E1, E2 and E3 were 0.018 ± 0.009, 0.025 ± 0.014 and 0.033 ± 0.019 L d(-1), respectively. Following field deployments of 28 days in the discharge of a sewage works, POCIS was shown to enhance the sensitivity of estrogen detection, especially for E3, and provide time-weighted average (TWA) concentrations of E1, E2 and E3, ranging from undetectable to 12 ng L(-1) upstream of the outflow of a sewage treatment works, 13 to 91 ng L(-1) at the outflow and 8 to 39 ng L(-1) downstream of the outflow. This revealed that E1, E2 and E3 are not completely removed during sewage treatment, with concentrations most likely being maintained by contributions from conjugated estrogen analogues. Grab water samples showed considerable variation in the concentrations of estrogens over a longer period (6 months). The results confirm that POCIS is an effective and non-discriminatory method for the detection of low concentrations of estrogens in the aquatic environment.     

Long-term changes of heavy metal and sulphur concentrations in ecosystems of the Taymyr Peninsula (Russian Federation) North of the Norilsk Industrial Complex

The Norilsk industrial ore smelting complex (Taymyr Peninsula, Russian Federation) has significantly impacted many components of local terrestrial and aquatic environments. Whether it has had a major impact on the wider Russian Arctic remains controversial as studies are scarce. From 1986 to 2004, data on heavy metal (Cu, Ni, Zn, Hg, Cd and Hg) concentrations in fish (burbot), moss, lichens, periphyton, hydric soils and snow in and around Norilsk and the most northern parts of the Taymyr Peninsula were analysed. Very high concentrations of Cu (203 μg L?1 ± 51 μg L?1) and Ni (113 μg L?1 ± 15 μg L?1) were found in the water of the Schuchya River close to Norilsk. Heavy metal concentrations in burbot liver were highest in Lake Pyasino near Norilsk compared to other study regions that were >100 km distant. From 1989-1996, Cu (121 μg L?1 ± 39 μg L?1 SD), Zn (150 μg L?1) ± 70 μg L?1) and Ni (149 μg L?1 ± 72 μg L?1) snow concentrations were greatest in Norilsk, but were low elsewhere. By 2004, these concentrations had dropped significantly, especially for Cu-74 μg L?1 (±18.7 μg L?1 SD), Zn-81.7 μg L?1 (± 31.3 μg L?1 SD) and Ni-80 μg L?1(±18.0 μg L?1 SD). Norilsk and its surroundings are subject to heavy pollution from the Norilsk metallurgical industry but these are absent from the greater Arctic region due to the prevailing winds and the Byrranga Mountains. Pollution abatement measures have been made so further investigations are necessary in order to assess their efficiency.     

Chemical techniques for assessing bioavailability of sediment-associated contaminants: SPME versus Tenax extraction

The traditional approach for predicting the risk of hydrophobic organic contaminants (HOCs) in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects to organisms. However, due to the multiple variables controlling bioavailability, this method has limitations. A matrix independent method of predicting bioavailability needs to be used in order to be universally applicable. Both chemical activity (freely dissolved chemical concentrations) measured by solid-phase microextraction (SPME) and bioaccessibility (rapidly desorbing fraction) estimated by Tenax extraction have been developed to predict bioavailability of sediment-associated HOCs. The objectives of this review are to summarize a number of studies using matrix-SPME or Tenax extraction to estimate bioavailability and/or toxicity of different classes of HOCs and evaluate the strengths and weakness of these two techniques. Although the two chemical techniques assess different components of the matrix, estimates obtained from both techniques have been correlated to organism body residues. The advantages of SPME fibers are their applicability for use in situ and their potential usage for a wide array of contaminants by selection of appropriate coatings. Single time-point Tenax extraction, however, is more time- and labor-effective. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants. This review also calls for additional research to evaluate the role of sequestrated contaminants and ingestion of sediment particles by organisms on HOC bioavailability. The use of performance reference compounds to reduce SPME sampling time and linking chemical based bioavailability estimates to toxicological endpoints are essential to expand the applications of these methods.     

Dietary exposure of three passerine species to PCDD/DFs from the Chippewa, Tittabawassee, and Saginaw River floodplains, Midland, Michigan, USA

Dietary exposure of house wrens (Troglodytes aedon), tree swallows (Tachycineta bicolor), and eastern bluebirds (Sialia sialis) to polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) near Midland, Michigan (USA) was evaluated based on site-specific data, including concentrations of residues in bolus samples and individual invertebrate orders and dietary compositions by study species. Site-specific dietary compositions for the three species were similar to those reported in the literature, but differed in their relative proportions of some dietary items. Oligocheata (non-depurated) and Brachycera (Diptera) contained the greatest average concentrations of ??PCDD/DFs of the major site-specific dietary items collected via food web-based sampling. Average ingestion values of ??PCDD/DFs from site-specific bolus-based and food web-based dietary concentrations for nestlings at study areas (SAs) were 6- to 20-fold and 2- to 9-fold greater than at proximally located reference areas (RAs), respectively. Average ingestion values of total 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ_WHO???Avian) from site-specific bolus-based and food web-based dietary concentrations for nestlings at SAs were 31- to 121-fold and 9- to 64-fold greater than at proximally located RAs, respectively. Estimates of ??PCDD/DFs and TEQ_WHO???Avian tissue concentrations based on nestling dietary exposures were greater than those measured. Plausible explanations include nestling metabolism of 2,3,7,8-tetrachlorodibenzofuran and assimilation rates of less than the 70% assumed to occur over the nestling growth period. Profiles of the relative concentrations of individual PCDD/DF congeners in samples of invertebrates and bolus at SAs on the Tittabawassee River downstream of the source of contamination were dominated by 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (22% to 44%) and 2,3,7,8-tetrachlorodibenzofuran (18% to 50%).     

Salinity variations in the water resources fed by the Etnean volcanic aquifers (Sicily, Italy): natural vs. anthropogenic causes

In this paper, in an attempt to reveal possible changes connected to natural or anthropogenic causes, the main results of hydrogeochemical monitoring carried out at Mount Etna are evaluated. We report on the salinity contents of the groundwaters that flow in fractured volcanics, which make up the flanks of the volcano. These waters, analyzed for major ion chemistry, were sampled regularly from 1994 to 2004. Basing on nonparametric Sen??s slope estimator, time series of groundwater composition reveal that the salinity of most of the Etnean aquifers increased by 0.5% to 3.5% each year during this period. This change in the water chemistry is clearly referable to the overexploitation of the aquifers. This increasing trend needs to be inverted urgently; otherwise, it will cause a shortage of water in the near future, because the maximum admissible concentration of salinity for drinking water will be exceeded.     

The fate of steroid estrogens: partitioning during wastewater treatment and onto river sediments

The partitioning of steroid estrogens in wastewater treatment and receiving waters is likely to influence their discharge to, and persistence in, the environment. This study investigated the partitioning behaviour of steroid estrogens in both laboratory and field studies. Partitioning onto activated sludge from laboratory-scale Husmann units was rapid with equilibrium achieved after 1 h. Sorption isotherms and Kd values decreased in the order 17??-ethinyl estradiol > 17??-estradiol > estrone > estriol without a sorption limit being achieved (1/n?>1). Samples from a wastewater treatment works indicated no accumulation of steroid estrogens in solids from primary or secondary biological treatment, however, a range of steroid estrogens were identified in sediment samples from the River Thames. This would indicate that partitioning in the environment may play a role in the long-term fate of estrogens, with an indication that they will be recalcitrant in anaerobic conditions.     

Adsorption study of 14C-paraquat in two Malaysian agricultural soils

The adsorption equilibrium time and effects of pH and concentration of ¹⁴C-labeled paraquat (1,1^??-dimethyl-4,4^??-bipyridylium dichloride) in two types of Malaysian soil were investigated. The soils used in the study were clay loam and clay soils from rice fields. Equilibrium studies of paraquat in a soil and pesticide solution were conducted. Adsorption equilibrium time was achieved within 2 h for both soil types. The amount of ¹⁴C-labeled paraquat adsorbed onto glass surfaces increased with increasing shaking time and remained constant after 10 h. It was found that paraquat adsorbed by the two soils was very similar: 51.73 (clay loam) and 51.59 ?? g g^???1 (clay) at 1 ?? g/ml. The adsorption of paraquat onto both types of soil was higher at high pH, and adsorption decreased with decreasing pH. At pH 11, the amounts of ¹⁴C-labeled paraquat adsorbed onto the clay loam and clay soil samples were 4.08 and 4.05 ?? g g^???1, respectively, whereas at pH 2, the amounts adsorbed were 3.72 and 3.57 ?? g g^???1, respectively. Results also suggested that paraquat sorption by soil is concentration dependent.     

Mangrove vulnerability modelling in parts of Western Niger Delta, Nigeria using satellite images, GIS techniques and Spatial Multi-Criteria Analysis (SMCA)

Mangroves are known for their global environmental and socioeconomic value. Despite their importance, mangrove like other ecosystems is now being threatened by natural and human-induced processes that damage them at alarming rates, thereby diminishing the limited number of existing mangrove vegetation. The development of a spatial vulnerability assessment model that takes into consideration environmental and socioeconomic criteria, in spatial and non-spatial formats has been attempted in this study. According to the model, 11 different input parameters are required in modelling mangrove vulnerability. These parameters and their effects on mangrove vulnerability were selected and weighted by experts in the related fields. Criteria identification and selection were mainly based on effects of environmental and socioeconomic changes associated with mangrove survival. The results obtained revealed the dominance of socioeconomic criteria such as population pressure and deforestation, with high vulnerability index of 0.75. The environmental criteria was broadly dispersed in the study area and represents vulnerability indices ranging from 0.00?C0.75. This category reflects the greater influence of pollutant input from oil wells and pipelines and minimal contribution from climatic factors. This project has integrated spatial management framework for mangrove vulnerability assessment that utilises information technology in conjunction with expert knowledge and multi-criteria analysis to aid planners and policy/ decision makers in the protection of this very fragile ecosystem.     

Solid-phase extraction using hierarchical organosilicates for enhanced detection of nitroenergetic targets

A novel porous organosilicate material was evaluated for application as a solid phase extraction sorbent for preconcentration of nitroenergetic targets from aqueous solution prior to HPLC analysis. The performance of the sorbent in spiked deionized water, groundwater, and surface water was evaluated. Targets considered included 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, RDX, HMX, and nitroglycerin. The sorbent was shown to provide improved performance over Sep-Pak RDX. The impact of complex matrices on target preconcentration by the sorbent was also found to be less dramatic than that observed for LiChrolut EN. The impact of changes in pH on target preconcentration was considered. Aqueous soil extracts generated from samples collected at sites of ordnance testing were also used to evaluate the materials. The results presented here demonstrate the potential of this novel sorbent for application as a solid phase extraction material for the preconcentration of nitroenergetic targets from aqueous solutions.