Stereoselective degradation of aqueous endosulfan in modular estuarine mesocosms: formation of endosulfan gamma-hydroxycarboxylate

Solutions of alpha-endosulfan, beta-endosulfan, and technical grade endosulfan (70alpha:30beta) were added to modular estuarine mesocosms; the kinetics and degradation products from each mesocosm are reported. The persistent product endosulfan sulfate was generated in all cases; however, its yield was approximately a factor of three higher from alpha-endosulfan relative to beta-endosulfan. Beta-endosulfan hydrolyzed faster than alpha-endosulfan to endosulfan diol, which then rapidly degraded to endosulfan ether, endosulfan alpha-hydroxyether (major product), and endosulfan lactone. The ring-opened form of the lactone, endosulfan gamma-hydroxycarboxylate, is reported for the first time; it appears to be a terminal product, at least over the timescale of the experiment. The equilibrium between endosulfan gamma-hydroxycarboxylate and endosulfan lactone is dependent on pH, as only the protonated form of the gamma-hydroxy acid undergoes ring-closure. The pKa of the gamma-hydroxy acid was determined to be 5.7, implying that the lactone will quickly open and deprontonate under environmentally relevant conditions.     

The fate and persistence of polychlorinated biphenyls in soil

The fate and persistence of PCBs 28, 52, 101, 138, and 180 artificially introduced into three soils was studied under a variety of field conditions for up to 415 d following initial contamination. A relationship was detected between ln Koa (octanol/air partition coefficient) and the experimentally observed first-order loss rate constant that was statistically significant at at least the 90% level in all but one instance. In nearly all experiments, PCB persistence was greater in soils of higher organic carbon content. Soil temperature and moisture content were also indicated as important influences on persistence. Significantly longer half-lives were observed in a soil in which initial PCB contamination had occurred ca. 1 year previously. A mass balance showed the most likely mechanism of loss to be volatilisation. Losses attributable to aerobic biodegradation could not be ruled out, but those due to leaching, uptake by biota, and soil erosion were demonstrated to be negligible. First-order rate constants (Kv) were determined for volatilisation of the same congeners from soil under a variety of controlled laboratory scenarios. Multiple linear regression analysis (MLRA) showed the most important influences on kv to be ln Koa (adjusted for soil temperature) and soil organic carbon content. Limited evidence was observed for a relationship between kv and soil moisture content, but not water flux. When tested against field measurements, the MLRA-derived relationship between kv and independent variables predicted to within a factor of 2.5, the persistence of PCBs 28, 52, and 101, However, it did not account for the influence of the age of contaminant association with the soil, soil moisture content or water flux, and failed to function for soils of high organic content, or where ln Koa exceeds ca. 23.     

Persistence of fipronil and its metabolites in soil under field conditions

Fipronil belongs to phenylpyrazole class of chemical compounds. Degradation of fipronil in sandy loam soil was investigated under field conditions by applying fipronil (Regent 5 % SC) at 50 (T ₁) and 100 g a.i. ha^?1 (T ₂) in field. Samples were drawn periodically in triplicate on 0 (1 h after treatment), 1, 3, 7, 10, 15, 30, 60, and 90 days after treatment and analyzed on GC-ECD system equipped with capillary column. The residues of fipronil in both the doses dissipated in the range of 93.33–100 % in 90 days. Limit of detection (LOD) and limit of determination (LODe/LOQ) were 0.0003 and 0.001 mg kg^?1, respectively. Dissipation followed a biphasic first-order kinetics with half-life values of 10.81 and 9.97 days for fipronil alone and 8.14 and 13.05 days for fipronil along with metabolites in soil at (T ₁) and (T ₂) treatments, respectively.     

Persistence and vertical distribution of termiticide fipronil in modified ground board test

Fipronil termiticide belongs to phenyl-pyrazole class of chemical compounds. It has broad-spectrum activity particularly against house hold pests such as cockroaches, mosquitoes, locusts, ticks, and fleas at both larval and adult stages. At high dosage it can be used to control subterranean termites in building foundations. To evaluate long term efficacy against termites the persistence and vertical distribution of fipronil was studied under natural weather conditions of Dehradun, India. Fipronil was applied at four concentrations i.e. 0.05, 0.1, 0.25 and 0.5% a.i ha⁻¹ by drenching 17 × 17 in.² plot prepared as per modified ground board test. Soil samples were collected after 22, 38 and 56 months of treatment up to the depth of 75 cm. The soil core was cut into five distinct sections i.e. 0–15, 15–30, 30–45, 45–60 and 60–75 cm depth. The residues were extracted by shaking 20 g soil sample with acetone. The acetone extract was concentrated and cleaned-up over florisil column. Fipronil residues were estimated on GLC at 220, 260, and 300°C oven, injector and detector temperature respectively. Fipronil was found to persist beyond 56 months after application. Two metabolites viz. desulfinyl and sulfide-fipronil were detected in sampling after 22 months of application that also dissipated with time. Fipronil residues were found up to 60 cm depth. The residues in deeper layers dissipate slowly with time and after 56 months of treatment residues were detected only up to 30 cm depth.     

The importance of considering spatial attributes in evaluating estuarine habitat condition: the South Carolina experience

The South Carolina Estuarine and Coastal Assessment Program (SCECAP) was initiated in 1999 to assess the condition of the state's coastal habitats using multiple measures of water quality, sediment quality, and biological condition. Sampling was subsequently expanded to include components required for the National Coastal Assessment (Coastal 2000) Program. Habitats are classified as either tidal creeks (<#60; 100 meters in width) or larger open water bodies. Approximately 30 sites are sampled within each habitat during the summer months using a probability-based random sampling design. Results obtained from the first two years of sampling documented significant differences in several water quality parameters (DO, salinity, pH, turbidity, fecal coliform bacteria, total nitrogen, TKN, total phosphorus) and biological measures (chlorophyll-a, finfish and crustacean abundance and biomass and a number of benthic species) between the tidal creek and open water habitats. These differences highlight the value of partitioning shallow water habitats separately from the larger open water bodies traditionally sampled in estuarine monitoring programs, especially since tidal creeks serve as critical nursery areas for many species. Based on the differences observed, there is a clear need to identify different physical and biological thresholds for evaluating the condition of each habitat type.     

The influence of estuarine water quality on cover of barnacles and Enteromorpha spp.

The influence of ambient water quality on the settlement of barnacles and the green alga Enteromorpha spp. to an artificial substratum in the estuaries of Sydney, Australia, was investigated to test the efficacy of both groups of organisms as indicators of changes in water quality due to urban stormwater runoff and/or sewage overflows. Wooden settlement panels were immersed for 4 months on 17 occasions between 1996 and 2005 at 11 locations known to vary in water-quality parameters (conductivity, total uncombined ammonia, oxidised nitrogen, total nitrogen, filterable phosphorus, total phosphorus, faecal coliforms and chlorophyll-a) and ambient meteorological conditions (total rainfall, maximum rainfall). Water-quality data were collected during the time that the settlement panels were deployed. Cover of barnacles was highly variable among locations (range 1.2?C55.2%). Hierarchical partitioning found that chlorophyll-a, total phosphorus and total nitrogen had significant independent positive effects on barnacle cover. Together, these variables explained 26% of the variation in barnacle cover. Mean cover of Enteromorpha spp., however, did not vary significantly among locations suggesting that other potentially more important factors are influencing its settlement and growth. The results of this study suggest that barnacle cover is likely to be a useful indicator of some components of water quality.     

Monitoring nekton as a bioindicator in shallow estuarine habitats

Long-term monitoring of estuarine nekton has many practical and ecological benefits but efforts are hampered by a lack of standardized sampling procedures. This study provides a rationale for monitoring nekton in shallow (<#60; 1 m), temperate, estuarine habitats and addresses some important issues that arise when developing monitoring protocols. Sampling in seagrass and salt marsh habitats is emphasized due to the susceptibility of each habitat to anthropogenic stress and to the abundant and rich nekton assemblages that each habitat supports. Extensive sampling with quantitative enclosure traps that estimate nekton density is suggested. These gears have a high capture efficiency in most habitats and are small enough (e.g., 1 m²) to permit sampling in specific microhabitats. Other aspects of nekton monitoring are discussed, including spatial and temporal sampling considerations, station selection, sample size estimation, and data collection and analysis. Developing and initiating long-term nekton monitoring programs will help evaluate natural and human-induced changes in estuarine nekton over time and advance our understanding of the interactions between nekton and the dynamic estuarine environment.     

The potential use of Atlantic silverside (Menidia menidia) for monitoring estuarine pollution

Monitoring chronic impacts of nearshore pollution on fish in Atlantic marine systems is challenging due to the mobility and seasonal nature of most habitat use. We evaluated Atlantic silverside (Menidia menidia) as a potential indicator of pollution across a gradient of contaminated sites in the Saint John River Estuary, New Brunswick, Canada. Fish returning from offshore in the spring showed no differences in length, weight, or condition factor between sites, but a graded response in condition factor appeared gradually, consistent with levels of contamination. Gonad size peaked in early June, however no differences in GSI were found among sites. By September, most fish collected were young of the year, with a significant bias towards female juveniles at the exposed site. These results indicate that Atlantic silverside are locally resident during their onshore period, and demonstrates their potential as a sentinel species. Sampling should focus on early June prior to the full moon to ensure maximal exposure periods before spawning, or in late October to evaluate growth as fish grow rapidly prior to offshore movement.     

Tracing the fate of PCBs in forest ecosystems

Forests were shown to play an important role in influencing atmospheric concentrations and transport of persistent organic pollutants (POPs) in the environment. World forests cover more than 4 billion hectares and contain up to 80% of the above ground organic carbon. Given the lipophilic nature of POPs, this suggests that forests can influence the environmental fate of POPs at a global scale. POP accumulation in forest canopies still presents points of concern given the complexity of these ecosystems. In particular, the role of ecological parameters such as LAI (leaf area index) and SLA (specific leaf area) and their dynamics during the growing season was not sufficiently investigated yet. This paper reviews, compares and interprets a unique case study in which air and leaf concentrations and deposition fluxes for selected polychlorinated biphenyls (PCBs) were measured in three different forest types exposed to the same air masses. In order to trace the air-leaf-soil path of these compounds, a dynamic model of POP accumulation into forest canopy was applied. The dynamics of the canopy biomass strongly affected the trend of leaf concentration with time. Growth dilution effect can prevent the more chlorinated compounds from reaching the partitioning equilibrium before litter fall, while the more volatile compounds can approach equilibrium in the range of few weeks. An amount of up to 60 ng of PCBs per square metre of ground surface was predicted to be stored in each of the selected forests at fully developed canopy. Dry gaseous deposition fluxes to forest canopy were estimated to reach a maximum value of about 0.5-1.5 ng m(-2) d(-1) during the spring period.     

Evaluation of environmental fate of acetamiprid in the laboratory

The acetamiprid, a nenicotinoid insecticide, is a popular crop protection agent used in fields as well as in protected cultivation. A laboratory experiment was conditions to study the effect of light, moisture, and pH on the persistence of acetamiprid in water and soil. Dissipation half-lives of acetamiprid in water at pH 4, 7, and 9 were 6.2, 7.3, and 5.1 days, respectively, and 4.3 days under UV and sunlight conditions. Half-life in soil at three concentrations, 0.1, 1.0, and 10 μg g^?1 under different moisture regimes varied from 21.5–22.8, 15.6–22.4, 10.0–15.8 days, respectively, indicating that acetamiprid dissipated faster in submerged soil as compared to field capacity moisture and dry conditions. The leaching study showed that the possibility for leaching of acetamiprid to ground water is extremely low under normal condition of average rainfall due to compact nature soil in the field. Acetamiprid poses low risks to the ecosystem because of their rapid dissipation and low-bound residues in the environment.     

The effects of opening an artificial tidal inlet on hydrography and estuarine macrofauna in Corpus Christi, Texas

Packery Channel is part of a complex of storm washover channels which, before 1912, have opened intermittently, linking the Laguna Madre and Corpus Christi Bay, Texas with the Gulf of Mexico. On 21 July 2005, with the assistance of Hurricane Emily, Packery Channel was prematurely opened to the Gulf of Mexico, months before construction of a dredged channel was scheduled to be completed. A before-versus-after, control-versus-impact (BACI) design was used to assess the effects of reopening Packery Channel on water quality and estuarine macrofauna in Mollie Beattie Coastal Habitat Community (MBCHC), Corpus Christi Bay. Two deep (approximately 1 m below m.s.l.) and two shallow (approximately 0.2 m below m.s.l.) stations were sampled monthly for physical and biological characteristics at both control and impact sites between November 2003 and March 2009. The opening of Packery Channel created a unique situation where salinities decreased after the channel opening by ameliorating hypersalinity in Laguna Madre rather than increasing salinities as would occur in most estuaries worldwide. Salinity also fluctuated in a diurnal pattern after the opening of Packery Channel. Apart from salinity, Packery Channel has caused little hydrographic change in MBCHC since opening in July 2005. There was little effect on the macrofaunal community composition. There was a greater difference in community composition between deep and shallow stations than between either before and after or control and impact sites. There have been no significant changes in abundance, biomass, or N1 diversity caused by the opening of Packery Channel.     

Transportation and fate of cationic surfactant in river water

The degradation, sorption, transportation and material balance of cationic surfactants discharged from domestic waste into river water was studied. Ion-pair solid-phase extraction behavior showed that the sorption of cationic surfactants as an ion-pair with anionic surfactant onto river sediment was so strong that little cationic surfactant was found in the bulk water. Cationic surfactant was found in river sediment at more than 500 times higher concentration than that in the bulk water. The degradation of the cationic surfactant was very slow in river water and much slower in the sediment. A material balance of cationic surfactant was estimated for a river running through Toyama City by measuring the flow rate and the concentration of cationic surfactant in the water at several points. It was found that more than 30% of cationic surfactant introduced to the river was lost during the river running through ca. 3 km in 3 h. This reduction probably comes from a quick transfer of the cationic surfactant from river water to sediment and water weed by means of adsorption or precipitation with suspending solids.     

The fate and behaviour of enhanced natural radioactivity with respect to environmental protection

In contrast to the monitoring and prevention of occupational radiation risk caused by enhanced natural radioactivity, relatively little attention has been paid to the environmental impact associated with residues containing enhanced activity concentration of naturally occurring radionuclides. Such materials are often deposited directly into the environment, a practice which is strictly forbidden in the management of other types of radioactive waste. In view of the new trends in radiation protection, the need to consider the occurrence of anthropogenically enhanced natural radioactivity as a particular unique case of environmental hazard is quite apparent. Residues containing high activity concentrations of some natural radionuclides differ from radioactive materials arising from the nuclear industry. In addition, the radiation risk is usually combined with the risk caused by other pollutants. As such and to date, there are no precise regulations regarding this matter and moreover, the non-nuclear industry is often not aware of potential environmental problems caused by natural radioactivity. This article discusses aspects of environmental radiation risks caused by anthropogenically enhanced natural radioactivity stored at unauthorised sites. Difficulties and inconclusiveness in the application of recommendations and models for radiation risk assessment are explored. General terms such as “environmental effects” and the basic parameters necessary to carry out consistent and comparable Environmental Risk Assessment (ERA) have been developed and defined.     

The burrowing crab Neohelice granulata as potential bioindicator of heavy metals in estuarine systems of the Atlantic coast of Argentina

This paper presents the concentrations of total copper, lead, cadmium, and zinc in hepatopancreas of the burrowing crab Neohelice granulata from the Samboromb??n Bay (La Plata River estuary) and the Mar Chiquita coastal lagoon, Argentina. The highest accumulation of lead was observed in Mar Chiquita samples, whereas copper, zinc, and cadmium concentrations were higher in those from Samboromb??n Bay. Marked temporal and geographic availability differences were observed, while sexual differences only were observed for zinc. Finally, the validity of using this species as bioindicator of heavy-metal pollution within the assessed estuarine ecosystems is discussed.     

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.     

Dissolved organic iodine in marine waters: role in the estuarine geochemistry of iodine

Non-volatile dissolved organic iodine (DOI) can be a major, or even the dominant, species of dissolved I in coastal, inshore and estuarine waters. It can be converted to IO3- in the presence of an oxidizing agent and to I- by reacting it with a reducing agent. Depending on the exact experimental conditions, the yields of these reactions may not be quantitative. In previous analytical schemes for the determination of IO3-, I- and DOI in marine waters, if oxidation or reduction steps are involved and the concentrations of one or more species are estimated by difference, the presence of DOI can lead to an overestimation of the concentrations of the inorganic species determined by difference and an underestimation of the concentration of DOI. In two cruises covering the James River to the southern Chesapeake Bay and from the southern Chesapeake Bay to the Atlantic, above a salinity (S) of 2, the contribution of DOI to total I increased with decreasing salinity and reached a maximum of 80%. DOI, I- and IO3- were successively the dominant form of dissolved I at 0.1 < S < 15 in the James River estuary, 15 < S < 30 in the Southern Chesapeake Bay and S > 30 in the Atlantic Ocean at the Bay mouth, respectively. Total I behaved conservatively (i.e., no evidence of consumption or production) during estuarine mixing during both cruises. In the southern Chesapeake Bay, total inorganic I was also approximately conservative. The primary process affecting the speciation of dissolved I was the conversion of IO3- to I-. In the James River estuary, there were indications of the conversion of both IO3- and I- to DOI. The concentrations of total I, IO3-, I- and DOI in James River water were 0.121, undetectable, 0.068 and 0.053 microM, respectively. These concentrations of total I and I- are significantly higher while that of IO3- is noticeably lower than those used presently for estimating global riverine input of these I species to the oceans. The riverine flux of DOI to the oceans is presently unknown.     

Simultaneous determination of insecticide fipronil and its metabolites in maize and soil by gas chromatography with electron capture detection

An integrated method for the simultaneous determination of insecticide fipronil and its three metabolites, desulfinyl, sulfide, and sulfone, in maize grain, maize stem, and soil was developed. This three-step method uses liquid–solid extraction with ultrasound or mechanical grinding, followed by liquid–liquid partitioning and florisil solid-phase extraction (SPE) for cleanup. The quantification was conducted by gas chromatography–electron capture detection in triplicate for each sample. The method was validated with five replicates at three fortification concentrations, 0.002, 0.01, and 0.1 mg kg^?1, in each matrix and gave mean recoveries from 83 to 106 % with relative standard deviation ≤8.9 %. The limits of quantification (LOQ) were 0.002 mg kg^?1 for the compounds in all matrixes. In the field study in Beijing and Shandong 2012, fipronil-coated maize seeds were planted and the proposed method was applied for checking the possible existence of four compounds in maize and soil samples, but none of them contained residues higher than the LOQs in both application rates. Moreover, the dissipation of fipronil in soil fits first-order kinetics with half-lives 9.90 and 10.34 days in Beijing and Shandong, respectively. Combined with an adequate sample treatment, this technique offers good sensitivity and selectivity in the three complex matrixes. The results could provide guidance for the further research on pesticide distribution and safe use of fipronil as seed coat in cereals.     

Monitoring of fate and effects of oil in the marine environment

Examples are presented of different techniques which are in use, or could be used, to monitor the fate and effects of oil pollution in Dutch marine waters by oil spills and chronic contamination by rivers, processing water from the oil industry, etc.A number of techniques are presented to quantify the fate of oil in water, sediments and biota, and some readily available methods to monitor possible effects in the ecosystem.In Dutch coastal waters much effort is being given to airborne detection of oil at the sea surface in order to reduce pollution and to take rapid measures in cases of severe pollution. Oil concentrations in sediments and selected organisms can be monitored as a general quality control measure, and to check the functioning of licensed installations. If concentrations above background levels are found, research on possible effects should be initiated. In this context short term studies on stress-indicators are very useful. Laboratory based investigations, for example in model ecosystems, can be carried out to test hypotheses from such studies. Elevated oil concentrations and indications for ecological effects may result in changes in the management of the marine area in question. Monitoring of population dynamics and species composition, notably of benthic macrofauna, should be carried out to verify long-term effects on the ecosystem.