Organohalogen contaminants in wildlife from the Yangtze River Delta : Development of methods and assessments of legacy and emerging persistent organic pollutants

Rapid economic development has occurred during the past few decades in China with the Yangtze River Delta (YRD) area as one of the most progressive areas. The urbanization, industrialization, agricultural and aquaculture activities result in extensive production and application of chemicals. Organohalogen contaminants (OHCs) have been widely used as i.e. pesticides, flame retardants and plasticizers. They are persistent, bioaccumulative and pose a potential threat to ecosystem and human health. However, limited research has been conducted in the YRD with respect to chemicals environmental exposure. The main objective of this thesis is to investigate the contamination level, distribution pattern and sources of OHCs in the YRD. Wildlife from different habitats are used to indicate the environmental pollution situation, and evaluate selected matrices for use in long term biomonitoring to determine the environmental stress the contamination may cause. In addition, a method is developed for dicofol analysis. Moreover, a specific effort is made to introduce statistic power analysis to assist in optimal sampling design. The thesis results show extensive contamination of OHCs in wildlife in the YRD. The occurrences of high concentrations of chlorinated paraffins (CPs) are reported in wildlife, in particular in terrestrial species, (i.e. short-tailed mamushi snake and peregrine falcon). Impurities and byproducts of pentachlorophenol products, i.e. polychlorinated diphenyl ethers (PCDEs) and hydroxylated polychlorinated diphenyl ethers (OH-PCDEs) are identified and reported for the first time in eggs from black-crowned night heron and whiskered tern. High concentrations of octachlorodibenzo-p-dioxin (OCDD) are determined in these samples. The toxic equivalents (TEQs) of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDFs) are at mean levels of 300 and 520 pg TEQ g-1lw (WHO2005 TEQ) in eggs from the two bird species, respectively. This is two orders of magnitude higher than European Union (EU) regulation limit in chicken eggs. Also, a novel pattern of polychlorinated biphenyls (PCBs) with octa- to decaCBs, contributing to as much as 20% of total PCBs therein, are reported in birds. The legacy POPs shows a common characteristic with relatively high level of organochlorine pesticides (i.e. DDT, hexacyclohexanes (HCHs) and Mirex), indicating historic applications. In contrast, rather low concentrations are shown of industrial chemicals such as PCBs and polybrominated diphenyl ethers (PBDEs). A refined and improved analytical method is developed to separate dicofol from its major decomposition compound, 4,4’-dichlorobenzophenone. Hence dicofol is possible to assess as such. Statistic power analysis demonstrates that sampling of sedentary species should be consistently spread over a larger area to monitor temporal trends of contaminants in a robust manner. The results presented in this thesis show high CPs and OCDD concentrations in wildlife. The levels and patterns of OHCs in YRD differ from other well studied areas of the world. This is likely due to the extensive production and use of chemicals in the YRD. The results strongly signal the need of research biomonitoring programs that meet the current situation of the YRD. Such programs will contribute to the management of chemicals and environment in YRD, with the potential to grow into the human health sector, and to expand to China as a whole.

Screening of pharmaceuticals and other pollutants of concern by a combination of chemical and biological methods

This study examined the occurrence of pharmaceuticals and personal care products (PPCP's) in surface waters of Florida and their potential to be use as indicators of wastewater contamination. Previous studies have shown that elimination of pharmaceuticals in municipal sewage treatment plants is often incomplete. Aquatic ecosystems are under increased stress from human activities, particularly in heavily populated areas. The purpose of this study was to find an ideal indicator for wastewater. The applied methods, GC/MS and LC/MS, were suitable for the determination of pharmaceuticals and personal care products in aqueous environmental samples to the lower parts-per-trillion (ng/L) level. As a result of this study a snapshot view of the occurrence of pharmaceuticals and personal care products in south Florida was produced. PPCP's were commonly detected in coastal environments of South Florida at relatively low concentrations. In general, PPCP's were higher inside the canals and contained bodies of water than in open water systems. Caffeine was successfully used to describe impacted versus pristine locations. However, no particular correlation was observed among caffeine and other traditional water quality parameters.

Assessment of silicone polymer composites for the trace extraction of herbicides : a tool for environmental forensics

Passive samplers are not only a versatile tool to integrate environmental concentrations of pollutants, but also to avoid the use of live sentinel organisms for environmental monitoring. This study introduced the use of magnetic silicone polymer composites (Fe-PDMS) as passive sampling media to pre-concentrate a wide range of analytes from environmental settings. The composite samplers were assessed for their accumulation properties by performing lab experiments with two model herbicides (Atrazine and Irgarol 1051) and evaluated for their uptake properties from environmental settings (waters and sediments). The Fe-PDMS composites showed good accumulation of herbicides and pesticides from both freshwater and saltwater settings and the accumulation mechanism was positively correlated with the log Kow value of individual analytes. Results from the studies show that these composites could be easily used for a wide number of applications such as monitoring, cleanup, and/or bioaccumulation modeling, and as a non-intrusive and nondestructive monitoring tool for environmental forensic purposes.

Monitoring pollutants in occupied spaces.

There is increasing evidence of a causal link between airborne particles and ill health and this study monitored the exposure to both airborne particles and the gas phase contaminants of environmental tobacco smoke (ETS) in a nightclub. The present study followed a number of pilot studies in which the human exposure to airborne particles in a nightclub was assessed and the spatio-temporal distribution of gas phase pollutants was evaluated in restaurants and pubs. The work reported here re-examined the nightclub environment and utilized concurrent and continuous monitoring using optical scattering samplers to measure particulates (PM10) together with multi-gas analysers. The analysis illustrated the highly episodic nature of both gaseous and particulate concentrations in both the dance floor and in the bar area but levels were well below the maximum recommended exposure levels. Short-term exposure to high concentrations may however be relevant when considering the possible toxic effects on biological systems. The results give an indication of the problems associated with achieving acceptable indoor air quality (IAQ) in a complex space and identified some of the problems inherent in the design and operation of ventilation systems for such spaces.

Human exposure to particulate and gaseous pollutants in a bar.

There is increasing evidence of a causal link between airborne particles and ill health and this study examined the exposure to both airborne particles and the gas phase contaminants of environmental tobacco smoke (ETS) in a bar. The work reported here utilized concurrent and continuous monitoring using real-time optical scattering personal samplers to record particulate (PM10) concentrations at two internal locations. Very high episodes were observed in seating areas compared with the bar area. A photo-acoustic multi-gas analyser was used to record the gas phases (CO and CO2) at eight different locations throughout the bar and showed little spatial variation. This gave a clear indication of the problems associated with achieving acceptable Indoor Air Quality in a public space and identified a fundamental problem with the simplistic design approach taken to ventilate the space. Both gaseous and particulate concentrations within the bar were below maximum recommended levels although the time-series analysis illustrated the highly episodic nature of this exposure.

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

An investigation on benthic macro-invertebrates species diversity as bio-indicators of environmental health in Bahrekan Bay

The purpose of this study was to evaluate benthic macro-invertebrates species diversity as bio-indicators of environmental health in Bahrekan bay (in the Northwest of Persian gulf). Seasonal sediments sampling along 5 transects, 15 stations at 4 replicates (3 replicates for macrobenthos and 1 replicate for sediment analysis) was done from November 2008 to August 2009 by 0.025 m2 Van Veen grab sampler. Physical and chemical parameters of water, grain size analysis, %TOM and Ni and Va concentrations of sediments were assessed through four seasons. Macrobenthic communities after staining and sorting, using stereomicroscope have been identified. Their density in every station and every season calculated. For using of AMBI index, identified macrobenthos according to their sensitivity to stressors and pollutants, categorized into 5 ecological groups and for using of Bentix index categorized into 3 ecological groups. The diversity indices and indicators that showing ecological status were calculated. Also, the differences between physiochemical parameters of sea water, sediments TOM% and grain size, diversity indices in stations and seasons were recorded (P=0.05). The correlation coefficient determined for all parameters. According to the results of grain size analysis, bottom grain size categorized as clay. Highest percent of TOM was belong to autumn (36.39±.075) and lowest was belong to summer (19.01±0.51). Also there was positive correlation (p=0.01) between %TOM and %Clay that showing sediments with lowest size containing highest amounts of organic matters. Ni concentrations in sediments (87.80±21.25)mg/kg showed the amounts over than standards levels but Va concentrations in sediments (53.54±17.60)mg/kg showed the amounts lower than standards level. The highest density of macrobenthos was recorded for summer (8254±485) N/m2 and the lowest density was recorded for spring (3775±172)N/m2. The highest annual density was belong to mollusca (81%) and then polycheates (13%), Others (4%) and crustaceae (2%). The highest diversity was recorded for winter (Simpson index: 0.13±0.01, H':3.47±0.06) and the lowest diversity recorded for autumn (Simpson index: 0.16±0.01, H':3.17±0.06). in all stations, the highest amount of Shanon index was belong to T2S3 station in summer (4.11± 0.32) and the lowest amount was belong to T1S1 station in autumn (2.42± 0.41). The annual mean of Simpson diversity index: (0.15 ±0.04) and Shanon diversity index (3.36±0.03), illustrated that macrobenthos in Bahrekan bay have a good variation. The results of Brilluin and N1 (Number of equally common species) indices confirm the results of Simpson index. For study on the regions that diversity has a little difference between stations, with use of Ni index, the degree of differences could be better ono recognizable. According to the results of AMBI index in all seasons (autumn: 0.46±0.03; summer: 0.22±0.01; annual mean:0.31±0.01) and standards (0.0

Agriculture, Environmental Incentive Payments, and Water Quality in the Chesapeake Bay

Nonpoint sources (NPS) pollution from agriculture is the leading source of water quality impairment in U.S. rivers and streams, and a major contributor to lakes, wetlands, estuaries and coastal waters (U.S. EPA 2016). Using data from a survey of farmers in Maryland, this dissertation examines the effects of a cost sharing policy designed to encourage adoption of conservation practices that reduce NPS pollution in the Chesapeake Bay watershed. This watershed is the site of the largest Total Maximum Daily Load (TMDL) implemented to date, making it an important setting in the U.S. for water quality policy. I study two main questions related to the reduction of NPS pollution from agriculture. First, I examine the issue of additionality of cost sharing payments by estimating the direct effect of cover crop cost sharing on the acres of cover crops, and the indirect effect of cover crop cost sharing on the acres of two other practices: conservation tillage and contour/strip cropping. A two-stage simultaneous equation approach is used to correct for voluntary self-selection into cost sharing programs and account for substitution effects among conservation practices. Quasi-random Halton sequences are employed to solve the system of equations for conservation practice acreage and to minimize the computational burden involved. By considering patterns of agronomic complementarity or substitution among conservation practices (Blum et al., 1997; USDA SARE, 2012), this analysis estimates water quality impacts of the crowding-in or crowding-out of private investment in conservation due to public incentive payments. Second, I connect the econometric behavioral results with model parameters from the EPA’s Chesapeake Bay Program to conduct a policy simulation on water quality effects. I expand the econometric model to also consider the potential loss of vegetative cover due to cropland incentive payments, or slippage (Lichtenberg and Smith-Ramirez, 2011). Econometric results are linked with the Chesapeake Bay Program watershed model to estimate the change in abatement levels and costs for nitrogen, phosphorus and sediment under various behavioral scenarios. Finally, I use inverse sampling weights to derive statewide abatement quantities and costs for each of these pollutants, comparing these with TMDL targets for agriculture in Maryland.

Fish Reproduction Is Disrupted upon Lifelong Exposure to Environmental PAHs Fractions Revealing Different Modes of Action

Polycyclic aromatic hydrocarbons (PAHs) constitute a large family of organic pollutants emitted in the environment as complex mixtures, the compositions of which depend on origin. Among a wide range of physiological defects, PAHs are suspected to be involved in disruption of reproduction. In an aquatic environment, the trophic route is an important source of chronic exposure to PAHs. Here, we performed trophic exposure of zebrafish to three fractions of different origin, one pyrolytic and two petrogenic. Produced diets contained PAHs at environmental concentrations. Reproductive traits were analyzed at individual, tissue and molecular levels. Reproductive success and cumulative eggs number were disrupted after exposure to all three fractions, albeit to various extents depending on the fraction and concentrations. Histological analyses revealed ovary maturation defects after exposure to all three fractions as well as degeneration after exposure to a pyrolytic fraction. In testis, hypoplasia was observed after exposure to petrogenic fractions. Genes expression analysis in gonads has allowed us to establish common pathways such as endocrine disruption or differentiation/maturation defects. Taken altogether, these results indicate that PAHs can indeed disrupt fish reproduction and that different fractions trigger different pathways resulting in different effects.

In Situ Observation of the Thermal Decomposition of Weddelite by Heating Stage Environmental Scanning Electron Microscopy

The morphological and chemical changes occurring during the thermal decomposition of weddelite, CaC2O4·2H2O, have been followed in real time in a heating stage attached to an Environmental Scanning Electron Microscope operating at a pressure of 2 Torr, with a heating rate of 10 °C/min and an equilibration time of approximately 10 min. The dehydration step around 120 °C and the loss of CO around 425 °C do not involve changes in morphology, but changes in the composition were observed. The final reaction of CaCO3 to CaO while evolving CO2 around 600 °C involved the formation of chains of very small oxide particles pseudomorphic to the original oxalate crystals. The change in chemical composition could only be observed after cooling the sample to 350 °C because of the effects of thermal radiation.