Remediating dicamba-contaminated water with zerovalent iron

Dicamba (3,6-dichloro-2-methoxybenzoicacid) is a highly mobile pre- and post-emergence herbicide that has been detected in ground water. We determined the potential of zerovalent iron (Fe0) to remediate water contaminated with dicamba and its common biological degradation product, 3,6-dichlorosalicylic acid (DCSA). Mixing an aqueous solution of 100 microM dicamba with 1.5% Fe0 (w/v) resulted in 80% loss of dicamba within 12 h. Solvent extraction of the Fe0 revealed that dicamba removal was primarily through adsorption; however when the Fe0 was augmented with Al or Fe(III) salts, dicamba was dechlorinated to an unidentified degradation product. In contrast to dicamba, Fe0 treatment of DCSA resulted in removal with some dechlorination observed. When DCSA was treated with Fe0 plus Al or Fe(III) salts, destruction was 100%. Extracts of this Fe0 treatment contained the same HPLC degradation peak observed with the Fe0 + Al or Fe(III) salt treatment of dicamba. Molecular modeling suggests that differences in removal and dechlorination rates between dicamba and DCSA may be related to the type of coordination complex formed on the iron surface. Experiments with 14C-labeled dicamba confirmed that Fe-adsorbed dicamba residues are available for subsequent biological mineralization (11% after 125 d). These results indicate that Fe0 could be potentially used to treat dicamba and DCSA-contaminated water.     

A comparison of meal size and feeding rate of the lysianassid amphipods Anonyx nugax,Onisimus (=Pseudalibrotus) litoralis and Orchomenella pinguis

Lysianassid amphipods were collected in 1987 from Frobisher Bay, Baffin Island, and from the Mingan Archipelago, Gulf of St Lawrence. Meal size and feeding rate of Anonyx nugax (Phipps), Onisimus (=Pseudalibrotus) litoralis (Krøyer) and Orchomenella pinguis (Boeck) were estimated directly, gravimetrically and/or from predictive equations. Size-specific ingestion was greatest in A. nugax, which fed swiftly and efficiently in comparison to O. litoralis and O. pinguis. These two latter species dispersed some bait while feeding and crawling on its surface. Groups of lysianassids fed more wastefully than single individuals. Meal size of females of O. litoralis decreased with increasing maturity, while berried females of O. pinguis consumed less food than mature males. Up to 30 d of starvation had no effect on survival and feeding ability of A. nugax, but 10 to 15 d of starvation dramatically reduced feeding ability or killed O. litoralis and O. pinguis. Differences between meal size, feeding rate and survival point to divergent feeding patterns, which also have been evidenced elsewhere by analysis of gut contents. O. litoralis and O. pinguis are best characterized as facultative scavengers, while large A. nugax are possibly obligate carnivores. Results emphasize the importance of lysianassid amphipods, particularly A. nugax, as bait stealers and as predators of commercial species trapped by various fishing gear.     

Catalytic oxidation of TNT by activated carbon

Activated carbon can remove 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene (TNB) from aqueous solution and promote oxidation of TNT. After equilibrating a 0.35 mM TNT solution with activated carbon (0.2-1% w/v), HPLC and GC/MS analysis confirmed the presence of 2,4,6-trinitrobenzaldehyde (TNBAld) and 2,4,6-trinitrobenzene (TNB), and provided strong evidence supporting 2,4,6-trinitrobenzyl alcohol (TNBAlc) as an intermediate of TNT oxidation. After 6 d, TNT and its oxidation products were strongly bound to the activated carbon, while TNB was extractable with acetonitrile. Observations indicate that activated carbon catalyzes TNT oxidation to TNBAlc, which is readily oxidized to TNBAld and TNB in the absence of activated carbon under dark conditions. While adsorbed TNB was extractable with acetonitrile, activated carbon promoted rapid TNT oxidation and formation of unextractable residues. Strong binding is attributed to catalyzed oxidation of the TNT methyl group, probably through a free radical mechanism, and subsequent chemisorption of oligomers and polymerized products that are not desorbed from micropores. Our observations indicate TNT oxidation and bound residue formation after sorption by activated carbon increases the effectiveness of activated carbon to decontaminate water.     

TNT and 4-amino-2,6-dinitrotoluene influence on germination and early seedling development of tall fescue

Cost-effective and environmentally acceptable methods are needed to remediate munitions-contaminated soil. Some perennial grass species are tolerant of soil contaminants and may promote remediation because of their high water use and extensive fibrous root systems. The effects of 2,4,6-trinitrotoluene (TNT) and its reduction product, 4-amino-2,6-dinitrotoluene (4ADNT), on germination and early seedling development of tall fescue (Festuca arundinacea Schreb.) were determined. Tall fescue seeds were germinated in nutrient-free agar containing 0-60 mg TNT litre(-1) or 0-15 mg 4ADNT litre(-1). Germination decreased linearly as TNT concentration increased but was not significantly affected by 4ADNT at these concentrations. Concentrations less than 30 mg TNT litre(-1) or 7.5 mg 4ADNT litre(-1) had little effect on seedling growth and development. Higher TNT or 4ADNT concentrations substantially delayed seedling development, caused abnormal radicle tissue development, and reduced secondary root and shoot growth. Seedling respiration rates decreased linearly with increasing TNT concentration. Experiments indicate that tall fescue may be grown in soils that maintain soil solution concentrations of 30 mg TNT litre(-1) or less.     

PRINCIPLES FOR INTERNATIONAL GROUND-WATER LAW (I)

International ground-water resources have not received their full share of legal investigation. This paper outlines some principles applicable to the development of international co-operation concerning this important resource, bearing in mind that ground and surface waters are the same resource. In the absence of positive international law covering ground-water resources, national laws are investigated to examine their suitability for adaptation to the international level. In a second paper, to be published in the next issue of the Forum , the interjurisdictional experience among federated states and among independent states will be reviewed.     

Transmitter attachment and release methods for short-term shark and stingray tracking on coral reefs

This study details a simple and cost-effective means of attaching acoustic transmitters to coral reef sharks and stingrays, which potentially allows for retrieval and reuse on completion of tracks. Between 2008 and 2011, galvanised timed releases were trialled in both static field tests and on blacktip reef sharks Carcharhinus melanopterus, cowtail Pastinachus atrus, and porcupine Urogymnus asperrimus rays in Coral Bay (?23°08′41″, 113°45′53″), Western Australia. The timed releases remained attached to animals for the duration required for tracking and in four out of five deployments transmitters were recovered after release from the animals. The use of modified Rototags for sharks and stainless steel darts for stingrays allowed rapid and effective attachment to animals, with limited impact on their welfare in the short term. External attachment for short-term tracking of coral reef-associated elasmobranchs should be considered as a complementary option to internal placement of transmitters in animals either by surgery or by ingestion.     

Transport of Sewage Sludge From the 106-Mile Site - Results From an October Survey

Abstract

Approximately 8 million tons of sewage sludge were disposed of annually at the 106-Mile Deepwater Municipal Sludge Dump Site (106-Mile Site) between 1987 and 1990. Beginning in 1988 and continuing to the present, the focus of monitoring at the 106-Mile Site moved towards improved understanding of the fate of the sludge. A survey conducted in October 1989 was designed to (1) detect the presence of any sludge particles that settle rapidly following disposal, (2) determine if sludge could be detected in the surface waters at locations away from the immediate disposal site, and (3) determine if water quality was degraded, by assessing whether the Environmental Protection Agency's marine water quality criteria were being exceeded.

The survey showed that the sludge does have a rapidly settling component composed of organic floc. mineral grains, and other heavy, gritlike particles, all of which are relatively large. These particles may settle at rates of between 8 and 180 m h^?1 and may reach the sea floor within 1 to 13 days following disposal. Even though a rapidly settling component is present in the sludge, a significant fraction of the sludge was detectable in the form of intact sludge plumes in the upper 35 m of the water column at least 15 km from the Site. in addition, unique tracers of sludge such as xylem tracheids and Clostridium perfringens plus elevated total suspended solids and trace metals concentrations, were found at locations up to 40 km from the Site. the presence of these tracers correspond with in situ transmissometry data suggesting that a fraction of the sludge was remaining in the near-surface waters above the seasonal pycnocline. Concentrations of metals were below EPA chronic marine water quality criteria, which indicates that the water quality downstream of the Site was not impaired. the detection of sludge downstream of the 106-Mile Site is consistent with the southwestward movement of the surface water mass during the survey, as recorded by satellite-tracked surface drifters and current vectors derived from a current meter moored at 100-m depth immediately west of the Site. Near-surface transport was generally towards the southwest at a speed of approximately 22 cm s^?1?.     

Enhancing metolachlor destruction rates with aluminum and iron salts during zerovalent iron treatment

Pesticide-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of zerovalent iron (Fe(0)) to dechlorinate metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methyl ethyl) acetamide] in the presence of aluminum and iron salts. By treating aqueous solutions of metolachlor with Fe(0), we found destruction kinetics were greatly enhanced when Al, Fe(II), or Fe(II) salts were added, with the following order of destruction kinetics observed: Al2(SO4)3 > AlCl3 > Fe2(SO4)3 > FeCl3. A common observation was the formation of green rusts, mixed Fe(II)-Fe(III) hydroxides with interlayer anions that impart a greenish-blue color. Central to the mechanism responsible for enhanced metolachlor loss may be the role these salts play in facilitating Fe(II) release. By tracking Al and Fe(II) in a Fe(0) + Al2(SO4)3 treatment of metolachlor, we observed that Al was readily sorbed by the corroding iron with a corresponding release of Fe(II). The manufacturing process used to produce the Fe(0) also profoundly affected destruction rates. Metolachlor destruction rates with salt-amended Fe(0) were greater with annealed iron (indirectly heated under a reducing atmosphere) than unannealed iron. Moreover, the optimum pH for metolachlor dechlorination in water and soil differed between iron sources (pH 3 for unannealed, pH 5 for annealed). Our results indicate that metolachlor destruction by Fe(0) treatment may be enhanced by adding Fe or Al salts and creating pH and redox conditions favoring the formation of green rusts.