Principal Biogeochemical Factors Affecting the Speciation And Transport of Mercury through the terrestrial environment

It is increasingly becoming known that mercury transport and speciation in the terrestrial environment play major roles in methyl-mercury bioaccumulation potential in surface water. This review discusses the principal biogeochemical reactions affecting the transport and speciation of mercury in the terrestrial watershed. The issues presented are mercury-ligand formation, mercury adsorption/desorption, and elemental mercury reduction and volatilization. In terrestrial environments, OH^–, Cl^– and S^– ions have the largest influence on ligand formation. Under oxidized surface soil conditions Hg(OH)₂, HgCl₂, HgOH⁺, HgS, and Hg⁰ are the predominant inorganic mercury forms. In reduced environments, common mercury forms are HgSH⁺, HgOHSH, and HgClSH. Many of these mercury forms are further bound to organic and inorganic ligands. Mercury adsorption to mineral and organic surfaces is mainly dictated by two factors: pH and dissolved ions. An increase in Cl^– concentration and a decrease in pH can, together or separately, decrease mercury adsorption. Clay and organic soils have the highest capability of adsorbing mercury. Important parameters that increase abiotic inorganic mercury reduction are availability of electron donors, low redox potential, and sunlight intensity. Primary factors that increase volatilization are soil permeability and temperature. A decrease in mercury adsorption and an increase in soil moisture will also increase volatilization. The effect of climate on biogeochemical reactions in the terrestrial watershed indicates mercury speciation and transport to receiving water will vary on a regional basis.     

Experimental analysis of the contribution of swimming and drifting to the displacement of reef fish larvae

The extent to which behaviour affects the dispersal of pelagic larvae in reef fishes has been a topic of major discussion among marine ecologists. Here, we experimentally quantified the extent to which the displacement of late-stage larvae of Abudefduf saxatilis is due to active movement (i.e. swimming) and drifting. We consider drifting as the component of larval displacement accounted for by the current. Drifting was quantified by comparing larval displacement to the displacement of passive particles in an extended flow chamber that gave larvae the free choice of swimming (i.e. swim with or against the current or not swim at all). We also determine whether drifting results from currents exceeding larval swimming capabilities or from the behavioural choice of larvae of not to swim against adverse currents. To do this, we compare the speeds of larval swimming in the extended flow chamber to those obtained in a smaller chamber in which larvae are behaviourally forced to swim due to space constraints and a retaining fence (most available data on larval swimming is based on this sort of chamber). Within the extended chamber, larvae tended to face the current and swim slower than it. This resulted in a net displacement increasingly determined by drifting. We also found that in the extended chamber, larvae swam at speeds between one and six times slower than the speeds they achieved in the “behaviourally modifying” smaller chamber. This suggests that the net displacement in the extended chamber was in part due to the behavioural choice of the larvae of not to swim. The importance of this “behavioural drifting” is discussed in terms of energy savings required for successful completion of the larval period and post-settlement survival. The idea that larvae may modulate their swimming behaviour raises caution for the use of published data regarding swimming capabilities of reef fish larvae when assessing the extent to which these fish actively affect their dispersal.     

Characterization of environmental water samples using strontium and lead stable isotope compositions

A simple procedure using both cation and anion exchange chromatography has been applied in the study of lead and strontium isotope composition in rain and stream water samples from remote catchments in Scotland. Whereas the soil released strontium to stream waters, lead was removed from rain water and the concentrations in stream waters were very low. Highly precise analysis by thermal ionisation mass spectrometry proved necessary in the determination of strontium isotope composition. The ⁸⁷Sr/⁸⁶Sr ratio in rain water was close to that of marine strontium but the ratios in stream waters were constant and highly characteristic for the stream. In the case of the stream at the Sourhope site, the ratio (0.70798 ± 0.00005) was less than that in rain water and probably resulted from the weathering of one specific mineral. The results suggested that the ⁸⁷Sr/⁸⁶Sr ratios could be used as a stable isotope tracer of waters and to provide information on the weathering processes. Two major anthropogenic components of lead were identified in water samples. One had its origin in petrol additives whereas the other was probably of industrial origin. The low ²⁰⁶Pb/²⁰⁷Pb ratios observed in stream waters confirmed the lead as being of anthropogenic origin and the data suggested that there was a movement, albeit very small, of lead from the soil to waters.     

PCBs and organochlorine pesticides in blubber biopsies from free-ranging St. Lawrence River Estuary beluga whales (Delphinapterus leucas), 1994-1998

For the first time, organochlorine (OC) contaminants were measured in blubber biopsies from free-ranging St. Lawrence River Estuary beluga whales (Delphinapterus leucas), to compare contaminant levels to those previously measured in dead stranded belugas. PCBs, DDTs, toxaphene and chlordane-related compounds were the major OC contaminants detected in 44 belugas biopsied in 1994-1998. SigmaPCB (the sum of 104 congeners) ranged from 2080 to 128,000 ng/g lipid in males (n=34; minimum estimated ages 8-22 years), and from 148 to 44,100 ng/g lipid in females (n=10; minimum estimated ages 7-22 years). The concentrations of PCBs and OC pesticides in the blubber of these whales overlapped those observed in stranded belugas from an earlier study, and demonstrated comparable age and sex-related trends. However, lower proportions of mirex, HCB, DDTs, and many of the highly chlorinated PCBs occurred in the biopsy samples compared to results for blubber from stranded carcasses. Most major OC compounds were present at lower concentrations in the biopsies, but this does not appear to be solely related to age differences between the two groups, or to emaciation in the stranded whales. Nor does it appear to be associated with the use of superficial biopsies, and the possible stratification of lipids and OCs in the blubber layer. Nevertheless, given these possible confounding factors, and the uncertainty in age estimates for the biopsied whales, the results point to the need for careful interpretation of biopsy results when comparing with data taken from the full depth of the blubber mantle in stranded whales. Taken together, results from both biopsied whales and previously studied stranded belugas indicate that PCB and OC pesticide contamination of St. Lawrence beluga whales may occur across a broader range of levels than previously thought, at least for males which formed the largest group in this study, possibly due to different degrees of dietary exposure. It also appears that measuring contaminant concentrations only in stranded whales, may overestimate OC levels in the population as a whole, especially for highly chlorinated OCs.     

Bioconcentration of superlipophilic persistent chemicals

According to present understanding, persistent superlipophilic chemicals — such as octachlorodibenzo-p-dioxin, octachlorodibenzofuran, Mirex etc — with log K_ow > 6 and cross sections > 9.5 Å, bioconcentrate in aquatic organisms only little from ambient water. The most convincing argument against it is that in bioconcentration experiments with superlipophilic chemicals amounts applied exceeded water solubility by several orders of magnitude. This paper describes various methods for determining bioconcentration factors (BCF) of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin, BCF values evaluated by these methods match well with those calculated by QSARs for fish and mussels based on log K_ow and water solubility. As expected, these BCF values exceed previous values by several orders of magnitude. For BCF evaluation of superlipophilic chemicals in aquatic organisms we recommend:

1. flow-through systems, kinetic method (OECD guideline No. 305 E)
2. ambient concentrations < water solubility
3. during the uptake and especially during the elimination phase no toxic effects of the test organisms should occur.

     

Spatial Convergence in Major Dissolved Ion Concentrations and Implications of Headwater Mining for Downstream Water Quality

Spatial patterns in major dissolved solute concentrations were examined to better understand impact of surface coal mining in headwaters on downstream water chemistry. Sixty sites were sampled seasonally from 2012 to 2014 in an eastern Kentucky watershed. Watershed areas (WA) ranged from 1.6 to 400.5 km² and were mostly forested (58%–95%), but some drained as much as 31% surface mining. Measures of total dissolved solutes and most component ions were positively correlated with mining. Analytes showed strong convergent spatial patterns with high variability in headwaters (<15 km² WA) that stabilized downstream (WA > 75 km²), indicating hydrologic mixing primarily controls downstream values. Mean headwater solute concentrations were a good predictor of downstream values, with % differences ranging from 0.55% (Na⁺) to 28.78% (Mg²⁺). In a mined scenario where all headwaters had impacts, downstream solute concentrations roughly doubled. Alternatively, if mining impacts to headwaters were minimized, downstream solute concentrations better approximated the 300 μS/cm conductivity criterion deemed protective of aquatic life. Temporal variability also had convergent spatial patterns and mined streams were less variable due to unnaturally stable hydrology. The highly conserved nature of dissolved solutes from mining activities and lack of viable treatment options suggest forested, unmined watersheds would provide dilution that would be protective of downstream aquatic life.     

Persistent organic pollutants,heavy metals and parasites in the glaucous gull (Larus hyperboreus) on Spitsbergen

The prediction of a higher parasite infection as a consequence of an impaired immune system with increasing persistent organic pollution (POP) and heavy metal levels were investigated in adult glaucous gull (Larus hyperboreus) from Svalbard. The levels of chlorinated pesticides, polychlorinated biphenyls (PCBs), toxaphenes and polybrominated diphenyl ethers (PBDEs) were measured in liver. Cupper, cadmium, lead, mercury, selenium and zinc were measured in kidney samples. An elevated ratio of PCB-118 was found, suggesting that local contamination from the settlement was detectable in the glaucous gull. Eight cestodes, four nematodes, two acanthocephalan and three trematode helminth species were found in the intestine. A positive correlation was found between cestode intensities and selenium levels and between acanthocephalan intensities and mercury levels. No correlation was found between parasite intensities and POP concentrations. It is concluded that the contaminant levels found in glaucous gulls do not cause immune suppression severe enough to affect parasite intensity.     

From Management to Negotiation: Technical and Institutional Innovations for Integrated Water Resource Management in the Upper Comoé River Basin, Burkina Faso

This study focuses on the potential role of technical and institutional innovations for improving water management in a multi-user context in Burkina Faso. We focus on a system centered on three reservoirs that capture the waters of the Upper Comoé River Basin and servicing a diversity of users, including a sugar manufacturing company, a urban water supply utility, a farmer cooperative, and other downstream users. Due to variable and declining rainfall and expanding users’ needs, drastic fluctuations in water supply and demand occur during each dry season. A decision support tool was developed through participatory research to enable users to assess the impact of alternative release and diversion schedules on deficits faced by each user. The tool is meant to be applied in the context of consultative planning by a local user committee that has been created by a new national integrated water management policy. We contend that both solid science and good governance are instrumental in realizing efficient and equitable water management and adaptation to climate variability and change. But, while modeling tools and negotiation platforms may assist users in managing climate risk, they also introduce additional uncertainties into the deliberative process. It is therefore imperative to understand how these technological and institutional innovations frame water use issues and decisions to ensure that such framing is consistent with the goals of integrated water resource management.