New Evidence for the presence of arsenocholine in shrimps (Pandalus borealis) by use of pyrolysis gas chromatography — atomic absorption spectrometry/mass spectrometry

An analytical method for the structure elucidation of quarternary organoarsenic compounds in trace amounts in fish and crustaceans has been developed in this laboratory. The two major organoarsenicals found in shrimps have been separated by ion-exchange chromatography and their stucture has been studied by the use of pyrolysis gas chromatography. Their degradation in the pyrolyzer unit has been studied by the use of atomic absorption spectrophotometer or mass spectrometer as detectors. A comparison of the analytical data of these substances and data from synthetic reference substances show complete agreement. The structures of reference compounds have been confirmed by use of nuclear magnetic resonance spectrometry and fast atom bombardment (FAB) mass spectrometry. It is demonstrated that both of the organoarsenic compounds in shrimps have a trimethylarsonio moiety e.g. the compounds have a quarternary structure. Furthermore, the more basic organoarsenic compound has a mass spectrometric fragmentation pattern similar to synthetic arsenocholine and acetylarsenocholine. Treatment of arsenobetaine with hot base produces trimethylarsineoxide in a high yield (96%). Arsenocholine, however, remains unchanged during this treatment. Treatment with sodium benzenethiolate does not result in chemical demethylation, which shows that this method together with gas chromatography-mass spectrometry is not feasible for confirmation of its structure.     

On-line speciation of arsenical compounds in fish and mussel extracts by HPLC-ICP-MS

The separation and determination of sub-μmol/l levels of six environmentally significant As compounds was accomplished by means of high performance liquid chromatography (HPLC) combined online with inductively coupled plasma mass spectrometry (ICP-MS). The species of interest (arsenite and arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine and arsenocholine) were quantified in fish and mussel extracts after separation on a Dionex AS7 column equipped with an on-guard AG7 column using a bicarbonate buffer as the mobile phase in a gradient mode. The species thus eluted were directly forwarded to the ICP-MS detector. The detection power of the overall system allows each As form to be determined at concentrations as low a 0.0013–0.0027 μmol 1⁻¹.     

Identification of arsenobetaine in sole,lemon sole,flounder, dab,carb and shrimps by field desorption and fast atom bombardment mass spectrometry

Organo-arsenic has been isolated from sole, lemon sole, flounder, dab, crab and shrimps by extraction or ion-exchange in combination with thin-layer chromatography. An alkaline digestion of the samples, followed by a reduction with sodiumborohydride leads to the formation of trimethylarsine. The behaviour of the organo-arsenic compound was very similar to that of synthesized arsenobetaine. Field desorption mass spectrometry (FDMS) can be used to identify arsenobetaine in the isolates. Sufficient purification by thin-layer chromatography is found to be a prerequisite for the detection of a protonated molecular ion of arsenobetaine. If this situation is not met acid enhanced FDMS or Fast Atom Bombardment mass spectrometry in high resolution can be used successfully.     

Effect of cadmium and zinc on intestinal absorption of xylose and tryptophan in the fresh water teleost fish, Heteropneustesfossilis

The effect of cadmium and of zinc on the rate of uptake of a pentose sugar xylose and an aminoacid tryptophan by the intestine of a teleost fish, $\text{Heteropneustes}$$\text{fossilis}$ was studied under two experimental conditions. In the first, four concentrations of cadmium or zinc (1.0 mM, 0.1 mM, 0.01 mM and 0.001 mM) mixed with the nutrient solution were filled in the intestinal sacs, and the rate of absorption was recorded after 1 h at 23°C. In the second experiment fish were exposed by bath to a sublethal concentration of cadmium (0.26 mg/1) or zinc (4 mg/1) for 15 and 30 days and the rate of absorption of the two nutrients was measured. The activity of intestinal Na⁺, K⁺ activated adenosine triphosphatase was also assayed. The two heavy metals at all the four concentrations decreased the rate of intestinal transport of nutrients. Increase in the concentration of each of the heavy metals decreased the uptake of nutrients, but the decreases were not linear. The rate of intestinal absorption of the two nutrients was also reduced by exposure of fish to the heavy metals $\text{in}$$\text{vivo}$. The activity of Na⁺, K⁺ ATPase decreased $\text{in}$$\text{vitro}$ with all four concentrations of cadmium and zinc and was diminished in fish exposed for 15 and 30 days. Of the two heavy metals, cadmium was more effective in reducing the rate of transport of xylose and tryptophan.     

Environmental dynamics of phosphate esters. III. Comparison of the bioconcentration of four triaryl phosphates by fish

Uptake, clearance and extent of metabolism of ¹⁴C-labelled t-butylphenyldiphenyl phosphate (t-BPDP), tri-m-cresyl phosphate (mTCP), tri-p-cresyl phosphate (pTCP) and triphenyl phosphate (TPP) were studied in rainbow trout ($\text{Salmo}$$\text{gairdneri}$) and fathead minnows ($\text{Pimephales}$$\text{promelas}$) using short-term static exposures (50 and 5 μmg/L). Bioconcentration factors for pTCP, mTCP, TPP and tBPDP calculated by use of total radioactivity in whole fish were 1420, 784, 573 and 1096 respectively, for rainbow trout and 928, 596, 561 and 1010 respectively, for fathead minnows. Differences in rates of clearance and biotransformation among the four compounds were more closely related to their ease of hydrolysis than to hydrophobicity.     

Biotransformation of N-phenyl-β-naphthylamine to β-naphthylamine in a laboratory sludge system

$\text{N}$-Phenyl-$\text{β}$-naphthylamine, a widely used rubber antioxidant and antiozonant, was biotransformed into $\text{β}$-naphthylamine, a potent carcinogen, in a laboratory sewage sludge system. $\text{β}$-Naphthylamine appeared to accumulate in the aqueous phase of the system while the undegraded parent compound appeared to be associated with the sludge solids.     

Arsenic speciation in field-collected and laboratory-exposed earthworms Lumbricus terrestris

Mature Lumbricus terrestris were host soils and leaf litter were collected from a former arsenic mine in Devon, UK (Devon Great Consols), a former gold mine in Ontario, Canada (Deloro), and an uncontaminated residential garden in Nottingham, UK. Arsenic concentrations determined by inductively coupled plasma-mass spectrometry (ICP-MS) in soils were 16-348 mg kg⁻¹, 6.0-239 mg kg⁻¹ in the earthworms and 8.6 mg kg⁻¹ in leaf litter sampled at Deloro (all dry weight). High performance liquid chromatography (HPLC-ICP-MS) analysis revealed arsenite (As^III), arsenate (As^V) and five organoarsenic species; arsenobetaine (AB), methylarsonate (MA^V), dimethylarsinate (DMA^V), arsenosugar 1 (glycerol sugar), arsenosugar 2 (phosphate sugar), and trimethylarsineoxide (TMAO) in field-collected L. terrestris. Differences were observed in the variety of organoarsenic species present between field sites. Several organoarsenic species were observed in the leaf litter (DMA^V, arsenosugar 2 and TMAO) but not AB. Depuration resulted in higher concentrations of inorganic As being detected in the earthworm whereas the concentration or variety of organoarsenic species was unchanged. Commercially sourced L. terrestris were exposed to As contaminated soil in laboratory mesocosms (1.0, 98, 183, 236, 324 and 436 mg kg⁻¹) without leaf litter and were additionally analyzed using X-ray absorption near edge structure (XANES). Only inorganic As^III and As^V was observed. It is proposed that ingestion of leaf litter and symbiotic processes in the natural soil environment are likely sources of organoarsenic compounds in field-collected L. terrestris.     

Bioaccumulation of pentachlorophenol by killifish (Fundulussimilus)

Killifish ($\text{Fundulus}$$\text{similis}$) were exposed in the laboratory to pentachlorophenol (PCP) at concentrations of 57 to 610 μg PCP/L. Bioaccumulation reached a plateau value of about 53 by 168 hrs and remained at this level for at least 72 hrs. One-half the plateau value was reached in about 25 hrs. Following exposure, fish placed in PCP-free aquaria lost PCP rather slowly ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 4.7}\text{days}$). The depuration data were suggestive of a pool of PCP which was lost more rapidly ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 4.2}\text{hrs}$). The results of this study are compared to similar studies in other species. The bioaccumulation factors measured in this study agree relatively well with those in other marine species, but are lower than reported for fresh water species. Possible reasons for this difference are discussed.     

Substitutes for phosphate containing washing products: Their toxicity and biodegradability in the aquatic environment

The toxicity of nitrolotriacetic acid (NTA), citrex-S-5, sodium alluminium silicate (NAS), carboxymethyloxysuccinate (CMOS), linear alkylbenzene sulfonate (LAS) and soap was examined using bacteria ($\text{Pseudomonas}$$\text{fluorescens}$), algae ($\text{Chlorella}$$\text{vulgaris}$ and $\text{Microcystis}$$\text{aeruginosa}$), crustaceans ($\text{Daphnia}$$\text{magna}$), insects ($\text{Aedes}$$\text{aegypti}$), fishes ($\text{Poecilia}$$\text{reticulata}$ and $\text{Oryzias}$$\text{latipes}$) and amphibians ($\text{Xenopus}$$\text{laevis}$). The biodegradability of NTA, citrex-S-5, CMOS and LAS was studied in the OECD-test.The acute toxicity of the compounds differed largely with the organisms tested (up to a factor 1,000). Based on the results of the short-term toxicity tests (with all test organisms) and the long-term toxicity tests (with $\text{Daphnia}$$\text{magna}$ and in case of LAS also with $\text{Poecilia}$$\text{reticulata}$) the following no-observed-effect concentrations (NOEC) could be derived: LAS 3.2 mg/1; NAS and soap 10 mg/1; CMOS 32 mg/1; NTA 100 mg/1 and citrex-S-5 320 mg/1. However, testing different samples of one test compound may result in marked differences in toxicity (e.g. NAS: a factor 32).All compounds tested showed to be biodegradable as the percentage DOC decreased more than 80% within four weeks. CMOS biodegraded quickly, whereas citrex-S-5 and LAS showed a somewhat slower rate of degradation. In contrast to the other compounds NTA required an adaptation period of 1 week.     

Photochemistry of 1-nitro-2-phenylnaphthalene available to the environment

Photolysis (254 nm, 72h) of 1-nitro-2-phenylnaphthalene $\text{1}$ in methanol gave 2-phenyl-1,4-naphthoquinone-4-monoxime $\text{2}$, 2,2′-diphenyl-4,4′-binaphth-1,1′-diol $\text{3}$ and 2,2′-diphenyl-4,4′-binaphth-1,1′-dione $\text{4}$. Straightforward reactions available to the environment account for the formation of the products: (a) isomerisation of the nitro compound into a nitrite ester followed by either (a) migration of the nitroso group and isomerisation into the oxime $\text{2}$ or (b) oxidative coupling and solvolysis into the binaphthol $\text{3}$ and followed by oxidation into the binaphthone $\text{4}$.     

Soluble carbohydrates in bean leaves transformed into oxidant-tolerant tissues by EDU treatment

Improved gas-liquid chromatography techniques were used to evaluate the effects of EDUa on soluble leaf carbohydrates in $\text{Phaseolus vulgaris}$ L. ‘Bush Blue Lake 290’. This snap bean cultivar is normally rather sensitive to 0₃ but becomes highly tolerant when treated systemically with EDU. Less than 24 h is required to induce the resistance. Standardized trifoliate leaves from EDU-treated and control plants were sampled 48 h after treatment. Additional plants were sampled 48 h after treatment. Additional plants were exposed to 0₃ one day after EDU soil application to assess the plant tolerance induced. The optimal dose required to enhance oxidant tolerance was 50 mg/pot.Major sugars in both EDU-treated (0₃-tolerant) and untreated (0₃-sensitive) leaves were glyceraldehyde, erythritol, fructose, glucose and sucrose. $\text{Myo}$-inositol, ribose and arbitol were present in lesser or trace amounts. EDU-treatment resulted in significant increases (35–62%) in all soluble carbohydrates except glyceraldehyde and $\text{myo}$-inositol. Implications relating to plant tolerance, to oxidants and stress-induced senescence are discussed.     

Partitioning of mercury in the North Saskatchewan River

Mercury levels in fish, water and sediments were determined during 1982 along a 600 km stretch of the North Saskatchewan River (NSR) in the province of Alberta. Migratory fish species such as goldeye, walleye and sauger in the NSR were found to contain total mercury levels ranging from 0.104 to 1.553 mg/kg ($\text{mean}\text{≧ 0.5}\text{mg}\text{/}\text{kg}$). Northern pike, white sucker, longnose sucker and northern redhorse sucker had total mercury levels ranging from 0.003 to 1.003 mg/kg (mean < 0.5 mg/kg) Regression analysis of the data revealed that neither the sex of the fish nor the location of the sampling site contributed significantly to the mercury burden in fish in the entire study section of the river. Sediment analysis showed a low and more or less uniform concentrations of mercury in Alberta (≦0.1 mg/kg). The total mercury in NSR water averaged 0.09 μg/L in upstream Edmonton and was found to elevate in downstream NSR (0.22 μg/L) near industrial discharge sites and agricultural runoff areas (mean = 0.20 μg/L). Calculated partition coefficients seem to group the fish into two categories, (i) goldeye, walleye and sauger (bioconcentration factor [BCF] =3?3.7×10³ and (ii) northern pike, longnose sucker, white sucker and northern redhorse sucker (BCF=1.2?1.8×10³).     

Removal of alpha-pinene from gases using biofilters containing fungi

Biofiltration is cost-effective for the treatment of gases containing low concentrations of volatile organic compounds $\text{(<3}\text{g}\text{m}{}^{\mathrm{-3}}\text{)}$. However, conventional biofilters, based on compost and bacterial activity, face problems with the elimination of hydrophobic compounds. Besides that, biofilter operational stability is often hampered by acidification and drying out of the filter bed. To overcome these problems, biofilters with fungi on inert packing material have been developed. Fungi are more resistant to acid and dry conditions than bacteria, and it is hypothesised that the aerial mycelia of fungi, which are in direct contact with the gas, can take up hydrophobic compounds faster than flat aqueous bacterial biofilm surfaces. Alpha-pinene was chosen as a model compound. It is an odorous compound emitted by the wood processing industry. In $\text{2}\text{l}$ biofilter columns four different packing materials were tested: perlite, expanded clay granules, polyurethane foam cubes and compost. The filters were inoculated with forest soil and ventilated with gas containing alpha-pinene. Start up took 1–2 months and removal efficiencies of more than 90% were observed, but mostly ranged from 50% to 90% due to overloading. In the filters containing perlite, clay, polyurethane and compost volumetric removal capacities of, respectively, 24, 33, 38 and $\text{24}\text{g}$ alpha-$\text{pinene}\text{m}{}^{\mathrm{-3}}$ filter $\text{bed}\text{h}{}^{\mathrm{-1}}$ were attained and the gas pressure drops in the $\text{60}\text{cm}$ high filter beds measured at a superficial gas velocity of $\text{35}\text{m}\text{h}{}^{\mathrm{-1}}$ were 70, 550, 180 and $\text{250}\text{Pa}$. The results indicate that it is possible to develop biofilters based on the action of fungi with higher elimination capacities for alpha-pinene as reported in literature for bacterial biofilters. The use of polyurethane foam cubes is preferred because of the low gas pressure drop in combination with a high volumetric elimination capacity.     

Hydrocarbons in Sand Crabs (Emeritaanaloga) from Southern California (U.S.A.)

$\text{Emerita}$$\text{analoga}$ (Crustacea:Hippidae) from three southern California (U.S.A.) beaches contained 0.9 to 24.1 μg/g dry wt saturated hydrocarbons, and 3.6 to 21.4 μg/g dry wt unsaturated hydrocarbons. Major constituents were (in wt. % total): n-alkanes (13.1%), heneicosapentaene plus heneicosahexaene (1.0%), squalene (5.1%), and unidentified polyenes (7.8%). Crabs from beaches exposed to small boat traffic and natural oil seepage were slightly and severely tainted, respectively, with petroleum hydrocarbons. Animals from San Nicolas Island (85 km offshore) contained only biogenic compounds.     

Uptake and degradation of trimethylamine by <Emphasis Type="Italic">Euphorbia milii</Emphasis>

Trimethylamine (TMA) is a volatile organic compound which causes not only unpleasant odor but also health concerns to humans. The average emission of TMA from food and fishery industries is 20.60 parts per billion (ppb) and emission from the gas exhausters is even higher which reaches 370 parts per million (ppm). In order to select the best plant TMA removal agent, in this study, 13 plants were exposed to 100 ppm of TMA and the remaining TMA concentration in their system was analyzed by gas chromatography (GC). Furthermore, plant metabolites from the selected plant were identified by gas chromatography-mass spectrometry (GC-MS). The result showed that Euphorbia milii was the most superior plant for TMA removal and could absorb up to 90 % of TMA within 12 h. E. milii absorbed TMA via leaf and stem with 55 and 45 % uptake efficiency, respectively. Based on its stomatal movement during the exposure to TMA, it was implied that the plant switched the photosynthetic mode from crassulacean acid metabolism (CAM)-cycling to CAM and CAM-idling. The switching of photosynthetic mode might reduce the stomata role in TMA absorption. Fatty acids, alkanes, and fatty alcohols in the plant leaf wax were also found to contribute to TMA adsorption. Leaf wax, stomata, and other leaf constituents contributed 58, 6, and 36 %, respectively, of the total TMA absorption by the leaf. The analysis and identification of plant metabolites confirmed that TMA was degraded and mineralized by E. milii.     

Chlordane compounds residues in Weddell seals (Leptonychotesweddelli) from the Antarctic

Weddell seal samples taken from the Antarctic have been found to be contaminated with chlordane compounds. ΣChlordane ($\text{cis}\text{-chlordane}\text{+}\text{cis}\text{-nonachlor}\text{+}\text{trans}\text{-nonachlor}\text{+}\text{oxychlordane}$) was present in blubber of seals at the range of 12 - 62 ng/g fresh weight. The order of chlordane compound concentrations was $\text{trans}\text{-nonachlor}\text{>}\text{oxychlordane}\text{>}\text{cis}\text{-nonachlor}\text{>}\text{cis}\text{-chlordane}$. Relative aboundance of $\text{cis}$-chlordane in Σchlordane is higher than that in humans. A probable explanation for their occurrence in the Antarctic is an airborne transport.     

Mercury induced alterations in the intestinal,absorption of nutrients in the fresh water murrel, Channapunctatus

The effect of five concentrations (10 mM, 1 mM, 0.1 mM, 0.01 mM and 0.001 mM) of mercury on the rate of absorption of glucose, fructose, glycine and tryptophan by the intestine of the fresh water murrel $\text{Channa}$$\text{punctatus}$ has been studied. Intestinal absorption of these nutrients was also examined in fish exposed to a sublethal concentration (3 μg/l) of mercury for 15 and 30 days. Significant decrease was recorded in the rate of intestinal absorption of all the four nutrients with higher concentrations (10 mM, 1 mM and 0.1 mM) of mercury. 0.01 mM and 0.001 mM of mercury also reduced the transport rate but it was insignificant, except in case of tryptophan, where 0.01 mM of mercury also produced significant decrease. Exposure of fish by bath to mercury also resulted in significant decrease in the intestinal transport rate of all the four nutrients after 30 days.     

The fate of dichlorvos in soil

Experiments were conducted to determine the factors responsible for the loss (adsorption, chemical hydrolysis, microbial degradation, etc.) of dichlorvos (2,2-dichlorovingl $\text{0}$,$\text{0}$-dimethyl phosphate) in soil perfusion systems of Houston Black clay. The rate of disappearance from the perfusate (hence the rate of dichlorvos degradation in soil) was related directly to the presence of $\text{Bacillus}$$\text{cereus}$ in the perfusion system, the pH of the system, and the extent of dichlorvos adsorption. Gas liquid chromatographic analyses of the perfusates showed that dichlorvos disappearance was rapid when $\text{B}$. $\text{cereus}$ was added to a previously sterilized soil perfusion system (50% in 3.9 days). Under sterile conditions, 50% of the added dichlorvos was recovered after 10 days. When $\text{B}$. $\text{cereus}$ was added to a mineral salts medium containing dichlorvos as sole ccrbon source, 49% of the initial dichlorvos concentration was degraded in 4 days. The organism was not capable of utilizing dichlorvos as a sole phosphorus source. Chemical hydrolysis of dichlorvos in aqueous, buffered, soil-free systems showed that hydrolysis did not occur in very acid systems (<pH 3.3), but increased with increasing pH values (26% in 4 days at pH 6.9), and was rapid at pH 9.3 (> 99% in 2 days). The extent of dichlorvos adsorption was determined by comparing the initial loss of dichlorvos in a sterile, soil-free extract solution with the initial loss in a sterile soil perfusion system. The rapid initial disappearance of dichlorvos in the presence of sterilized soil was attributed to soil adsorption of the pesticide. After 10 days both systems contained equal concentrations (50%) of dichlorvos. Non-biological mechanisms accounted for 70% of the total degradation of dichlorvos, while bacterial degradation accounted for 30% in the soil perfusion systems.     

Measurement of arsenic compounds in littoral zone algae from the Western Mediterranean Sea. Occurrence of arsenobetaine

The determination of arsenic compounds in algae collected on the Catalan coast (Western Mediterranean) is reported. Ten algae species and the seagrass Posidonia oceanica were analyzed. Total arsenic in the samples was determined by microwave digestion and inductively coupled plasma mass spectrometry (ICPMS). Arsenic speciation in water extracts of samples was analyzed by liquid chromatography with both anionic and cationic exchange with ICPMS detection (LC-ICPMS). The total arsenic content of the algae samples ranged from 2.96 to 39.0mg As kg(-1). The following compounds were detected: arsenite (As(III)), arsenate (As(V)), methylarsonate (MA), dimethylarsinate (DMA), sulfonate sugar (SO3-sug), sulfate sugar (SO4-sug), phosphate sugar (PO4-sug), arsenobetaine (AB), arsenocholine (AC), trimethylarsine oxide (TMAO) and glycerol sugar (Gly-sug). The main arsenic species found were arsenosugars. Significant percentages of arsenobetaine (0.54 mg As kg(-1), 28% of the extractable arsenic and 0.39 mg As kg(-1), 18% of the extractable arsenic) were found in Ulva rigida and Enteromorpha compressa. These results are discussed in relation to the presence of epiphytes.