A ten year summary of concurrent ambient water column and sediment toxicity tests in the Chesapeake Bay watershed: 1990-1999

The goal of this study was to identify the relative toxicity ofambient areas in the Chesapeake Bay watershed by using a suiteof concurrent water column and sediment toxicity tests at seventy-five ambient stations in 20 Chesapeake Bay rivers from1990 through 1999. Spatial and temporal variability was examinedat selected locations throughout the 10 yr study. Inorganicand organic contaminants were evaluated in ambient water andsediment concurrently with water column and sediment tests toassess possible causes of toxicity although absolute causalitycan not be established. Multivariate statistical analysis wasused to develop a multiple endpoint toxicity index (TOX-INDEX) at each station for both water column and sediment toxicity data. Water column tests from the 10 yr testing period showed that49% of the time, some degree of toxicity was reported. The mosttoxic sites based on water column results were located inurbanized areas such as the Anacostia River, Elizabeth River andthe Middle River. Water quality criteria for copper, lead,mercury, nickel and zinc were exceeded at one or more of thesesites. Water column toxicity was also reported in localizedareas of the South and Chester Rivers. Both spatial and temporalvariability was reported from the suite of water column toxicitytests. Some degree of sediment toxicity was reported from 62% of the tests conducted during the ten year period. The ElizabethRiver and Baltimore Harbor stations were reported as the most toxic areas based on sediment results.Sediment toxicity guidelines were exceeded for one or more of thefollowing metals at these two locations: arsenic, cadmium,chromium, copper, lead, nickel and zinc. At the Elizabeth Riverstations nine of sixteen semi-volatile organics and two of sevenpesticides measured exceeded the ER-M values in 1990. Ambientsediment toxicity tests in the Elizabeth River in 1996 showedreduced toxicity. Various semi-volatile organics exceeded the ER-M values at a number of Baltimore Harbor sites; pyrene anddibenzo(a,h)anthracene were particularly high at one of thestations (Northwest Harbor). Localized sediment toxicity was alsoreported in the Chester, James, Magothy, Rappahannock, andPotomac Rivers but the link with contaminants was not determined.Both spatial and temporal variability was less for sedimenttoxicity data when compared with water column toxicity data. Acomparison of water column and sediment toxicity data for thevarious stations over the 10 yr study showed that approximatelyhalf the time agreement occurred (either both suite of testsshowed toxicity or neither suite of tests showed toxicity).     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Monitoring atmospheric metal pollution: a review of the use of mosses as indicators

This article reviews the literatureon the use of mosses for monitoring atmospheric metalpollution. It discusses the nature of mosses, themechanisms for moss uptake of metals from the air andwet precipitation, the various forms in which mossesare used for this purpose, and cases in which mosseshave been used for monitoring local hot spots ofpollution, and regional patterns of metal pollution.Also highlighted are the questions of uptake of metalsfrom the substrates, interspecies differences, and acomparison of the effectiveness of mosses with otherindicator materials, among other issues.     

Influence of environmental parameters on the accuracy of nitrogen dioxide passive diffusion tubes for ambient measurement

Two studies at three sites in the UK provided confirmation that systematic positive bias in NO2 diffusion tube measurement occurred because of changes to "within-tube" chemistry, rather than eddy diffusion at the mouth of the tube. In the first study in Cambridge, UK, sampler overestimation for 1 and 2 week exposures was compared to corresponding time-averaged monitor measurements (NO-NO2-NOx, O3) and weather variables. Noninearity between sampler and monitor NO2 measurements was interpreted in terms of spatial and temporal variations in relative and absolute availability of NO, NO2 and O3 at the site. A maximum overestimation occurred for an exposure mean NO2/NOx approximately 0.5. The separate contributions of reduced NO2 photolysis and eddy diffusion were compared in Study II using samplers of two materials, acrylic and quartz, and of different lengths (40, 55, 71 and 120 mm) at three sites: Norwich background, Cambridge intermediate, London kerbside. For compared sites, NO2 measured by acrylic samplers was significantly higher than for equivalent quartz samplers. For quartz samplers [NO2]mean was only just above the monitor at Norwich and London; sampler/monitor NO2 = 1.04 (P = 0.59) and 1.01(P = 0.76), respectively. For acrylic samplers the order of [NO2]mean was 40 mm > 120 mm > 71 mm > or = 55 mm. Excepting 40 mm samplers, this accords with a chemical bias where co-diffusing NO and 03 molecules in longer tubes have more time to react to form excess NO2. Bias in 40 mm samplers is discussed. Eddy diffusion is negligible for standard samplers because [NO2]mean was equivalent for 55 mm and 71 mm acrylic samplers and close to monitor NO2 for 71 mm quartz tubes. Both studies showed that sampler accuracy was dependent on location. Significantly, overestimation was greatest (approximately 3-4 ppb) where the NO2 annual mean was approximately 20 ppb, close to the UK and EU air quality standard of 21 ppb.     

Assessing the Effects of Atmospheric Ethylene on Epinasty and Tuber Yield of Potato (Solanum Tuberosum L.) Near Polyethylene Manufacturing Plants

A multi-year programme was performed to assess the effects of atmospheric ethylene on potato (Solanum tuberosum L.) in the vicinity of polyethylene manufacturing plants. There was a strong temporal variation of the hourly ethylene concentrations measured close to the sources from 1982 through 1991. Growing seasonal means exceeded 12 g m^–3 ethylene, the threshold for phytotoxic effects under laboratory conditions. Young test plants of potato showed an epinastic response to enhanced levels of ethylene. This response was reversible and did not occur when atmospheric ethylene was not detected. Based on hourly observations for the growing seasons of 1984 through 1991, epinasty occurred on average during circa 5% of the growing season and varied from circa 1% in 1985 to circa 18% in 1991. At night, ethylene concentrations were higher and epinasty was more frequent than during daylight hours. The intermittent exposures to ethylene did not affect tuber yield for the growing seasons of 1982 through 1990. The occurrence of epinasty indicated that ethylene exposure levels in the vicinity of the industrial sources might be sufficiently high to affect sensitive plants.     

Degradability and Sediment Sorption of an Alcohol Polyglycol Ether Surfactant Putatively Useful for the Control of Red Swamp Crayfish in Rice Fields

This work reports studies of the degradation rates of a fattyalcohol polyglycol ether non-ionic surfactant, Genapol OXD-080, putatively useful for the control of red swamp crayfish (Procambarus clarkii Girard) in rice fields under laboratory and field conditions. The influence of temperature,sediment site specificity and sorption were taken into account.The degradation kinetics of the surfactant depends on the experimental conditions: type of inocula and temperature. Thedistribution of this chemical in aquatic systems was also examined. Genapol OXD-080 was removed into the sedimentsreadily after application, and sorption was considered the majorpath of removal from the water phase. Data suggest that furtherstudies are required regarding the effects of Genapol OXD-080 in aquatic organisms resident in rice fields, in parallelwith the development of technologies related with the use ofsurfactants to control P. clarkii populations.     

Modelling of Materials Policies

This paper discusses the REAP1 model and its application for the analysis of CO₂ reduction and waste management policies for Japanese petrochemicals. The pros and cons of this modelling approach in comparison to other tools is elaborated. This is followed by a discussion of the model code and the modelling results. The results show that CO₂ policies can have significant impacts on waste flows and waste policies can have significant CO₂ benefits. As a consequence both effects must be considered in policy assessment. Pricing instruments are recommended instead of regulations because of the complex physical relations in the materials life cycle that extend beyond sector boundaries. A taxation approach is superior to a subsidy approach because rebound effects can be avoided.     

Chromium speciation and fractionation in ground and surface waters in the vicinity of chromite ore processing residue disposal sites

Chromium concentrations of up to 91 mg l(-1) were found by ICP-OES for ground water from nine boreholes at four landfill sites in an area of S.E. Glasgow/S. Lanarkshire where high-lime chromite ore processing residue (COPR) from a local chemical works had been deposited from 1830 to 1968. Surface water concentrations of up to 6.7 mg l(-1) in a local tributary stream fell to 0.11 mg l(-1) in the River Clyde. Two independent techniques of complexation/colorimetry and speciated isotope dilution mass spectrometry (SIDMS) showed that Cr was predominantly (>90%) in hexavalent form (CrVI) as CrO4(2-), as anticipated at the high pH (7.5-12.5) of the sites. Some differences between the implied and directly determined concentrations of dissolved CrIII, however, appeared related to the total organic carbon (TOC) content. This was most significant for the ground water from one borehole that had the highest TOC concentration of 300 mg l(-1) and at which < 3% of Cr was in the form of CrVI. Subsequent ultrafiltration produced significant decreases in Cr concentration with decreasing size fractions, e.g. <0.45 microm, < 100 kDa, <30 kDa and < 1 kDa by the tangential-flow method. As this appeared related more to concentrations of humic substances than of TOC per se, horizontal bed gel electrophoresis of freeze-dried ultrafilter retentates was carried out to further characterise the CrIII-organic complex. This showed for the main Cr-containing fraction, 100 kDa-0.45 microm, that the Cr was associated with a dark brown band characteristic of organic (humic) matter. Comparison of gel electrophoresis and FTIR results for ultrafilter retentates of ground water from this borehole with those for a borehole at another site where CrVI predominated suggested the influence of carboxylate groups, both in reducing CrVI and in forming soluble CrIII-humic complexes. The implications of this for remediation strategies (especially those based on the addition of organic matter) designed to reduce highly mobile and carcinogenic Cr(VI)O4(2-) to the much less harmful CrIII as insoluble Cr(OH)3 are discussed.     

Distribution of Chlorinated Organic Pollutants in Harbor Sediments of Livorno (Italy): A Multivariate Approach to Evaluate Dredging Sediments

Dredging is a very important procedure for harbor management. InItaly the guidelines for the offshore dumping of dredged materials are issued by the Ministry of Environment. Theydescribed a few steps of dredging activities, such as thesampling strategy, but do not deal with limits or guide-valuesfor the chemical, physical and biological composition of theresulting sediments. The quality of dredged materials is mainlydependent on the presence of inorganic and organic pollutants.In particular, polychlorinated biphenyls (PCBs) and organo-chlorinated pesticides are seen as a high priority inmarine environment by international organizations because oftheir persistence, toxicity and bioaccumulation capacity.In this article the presence of some PCBs and organo-chlorinatedpesticides in sediment samples collected from the harbor ofLivorno (Northern Tyrrhenian Sea) was investigated. Theconcentration of HCHs, Aldrin, Chlordanes, DDEs, DDTs, and PCBsin 12 representative sites ranged between <1 g kg^–1and 95, 19, 32, 35, 107, and 111 g kg^–1, respectively.The application of univariate and multivariate statisticaltechniques, such as linear regression analysis and principalcomponent analysis, to the experimental data showed a differentdistribution of PCBs in the two sediment layers. On thecontrary, the vertical distribution of the other investigatedpollutants was more homogeneous and affected by randomvariability. The multivariate approach was an important tool to establish more rational criteria for the management of dredged materials.     

Nitrogen isotope ratios in pine bark as an indicator of N emissions from anthropogenic sources

The article describes the use of Scots pine bark to identifynitrogen sources in eastern Germany, as well as background areas in Russia and Bulgaria, by using natural isotope ratios of total nitrogen (N_t) and individual N compoundssuch as ammonium (NH₄ ⁺), nitrate (NO₃ ^-)and amid nitrogen (amide-N). The samples collected were analysed using an elemental analyser in connection with a gas isotope mass spectrometer (EA-IRMS). Natural ¹⁵N abundances in pine bark from impact areas suggest that the ammonium accumulated on the surface of the bark is releasedfrom livestock management. Bark of Scots pines growing near agricultural land had highly depleted ¹⁵N_t values (between –8 and –12), while bark from background areas (unpolluted areas) displayed slightly negative ¹⁵N_t values (mean ¹⁵N_t = –3.8). It is assumed that part of the N adsorbed on the bark surface is mainly derived from ammonia(mean ¹⁵N_t = –40.3) escaping from livestock housing and during the application of manure. This assumption is confirmed by experiments under controlled conditions in which manure samples were spread on soil. In addition, temporal and spatial variations of ¹⁵N_t abundances in pine bark from various locations in eastern Germany as wellas pine stands in Nature Park Dübener Heath are discussed.