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Sea birds, particularly " Duikers. Seals, Porpoises and Sharks. Escape of injurious matter from wrecks, g. Fresh water in tidal rivers. Use of American purse-net. Capture of immature fish. Red water. Obscure causes, such as earthquakes, cold currents, etc. Some thirty years ago the [C. It appears at first sight that the contention is hardly justifiable, and, indeed, was received with a good deal of incredubiUty if not ridicule by the public generally.

It seems not improbable, however, that there may be some truth in the allegation of the fishermen, with reference at least to one kind of fish : this is the Harder or Mullet, which is one of the most important to fishermen on the stretch of coast line referred to. Its habits are well known to fishermen, and the presence of a shoal of these fish can be detected at a distance of some miles by the man stationed at the look-out, generally some elevated position on the mountain side.

When on the move along the shore, it has been observed that the fish are very readily alarmed, and make off to the open sea, in fact, as will be noted later, they can be driven off by the splashing of oars, and it is said that they can even detect the putting out of the trek boat, if incautiously done.

It is not surprising, therefore, that, as has been observed by the fishermen, a shoal, for which they are waiting, is driven off by the vibration of a heavy train, only a few hundred yards distance. There seems no reason to believe, however, that any permanent injury is done. It is true that it is just along this shore — Simon's Town to Muizenberg — that anglers also state that fish, such as Galjoen, Hottentot and other such species have, of recent years, been much scarcer, but, in judging of the value of this evidence, it is to be remembered that it is this locality that is chiefly visited by anglers, and the same complaint of scarcity of fish is heard from anglers at other localities, where no trains run, as will be seen later on.

It is also stated by fishermen that the firing of heavy guns from forts and warships, particularly at the naval station at Simon's Town, has a bad effect on fishing, but this does not seem to have been substantiated by any very definite evidence, and in any case is on a footing with the alleged damage done by train, in so far as it is a purely local occurrence. The explosion of a shell in the water might be supposed to have the same effect as dynamiting, but this does not seem to have been observed.

The use of dynamite for the capture of fish is an obvious cause of very serious destruction of fish life, and is universally II condemned. It need not, however, be dealt with in this enquiry, as it has long ago in been prohibited by law, and there is no reason to believe such a wasteful method of procuring fish is indulged in to any extent, though now and again it may be employed in some of the up-country rivers and pools near mining operations.

The fish supply is said to have been affected in nearly all countries by the increase of shipping, especially of steamers, at the large ports, and South Africa is not an exception in this respect. In Table Bay more particularly, where the increase of shipping has chiefly occurred, the alleged diminution of fish has been associated with the increased traffic. This, hke the running of trains and firing of guns, is of local occur- rence, and, if fish are scared away, it is probably only to some other part of the coast.

Differing from these is the allegation that netting, especi- ally at certain times and places, is responsible for such diminu- tion. The consideration of this is of more importance than any of the above, as not only does it occur on a larger scale, but it can be more or less remedied. Objections to netting in South Africa were first put forward at Port Elizabeth in connection with fishing in the Zwartkops River, which opens into Algoa Bay near that town.

The river is tidal for several miles inland, and is a favourite resort for anglers as well as netters. Netting was not carried on on an extensive scale, only one or two fishers catching fish for sale. It was alleged by the anglers that, in netting operations, quantities of fish spawn and young were destroyed, that the fish came into the river to breed, and were unduly disturbed by the netters, and that as a consequence fish were becoming scarcer in the river.

The netters, on the other hand, stated that their operations were an actual benefit to the fish supply, as they frequently caught large sharks, one of which could cause more damage than all the netters together. They stated, furthermore, that there was no evidence of the diminution of fish and that the fish came out and in with every tide.

For further discussion of this question vide p. The destruction of fish by sea birds must be enormous. Malagas, Duikers and Penguins live on fish, and, on the West coast of South Afiica, where these birds breed without disturb- ance on the small islands off the coast, they occur in large numbers. They are protected from their enemies by being able to resort in the breeding season to these barren islands, on which no natural enemies, such as jackals or other carnivora of the mainland, can exist.

They are now further protected by legislation, as they are most valuable guano producers. The chief offender amongst these birds is the " Cormorant," [C. It is a well-known enemy of fish everywhere and, in some countries, rewards are offered for the destruction of these pests of the fishermen. Unfortunately, in South Africa, it is the best producer of guano, and thus arises the conflict between the interests of the fisher- men and the farmers, who obtain from Government this valuable fertilizer at a rate less than the open market value.

These birds are rigorously protected by law, landing on the islands being prohibited, especially during the breeding season. The fishermen seem to have, therefore good cause for their complaints, as this protection of the chief enemies of fish will naturally be detrimental to the fishing industry. That the Duiker is a very expert fisher was very clearly demonstrated on one occasion at the Marine Laboratory at vSt.

At times the bird seems to be affected by some illness, which causes it to seek the shore, and isolated indi- viduals may be seen perched on some rock where they can be readily approached. On one occasion a Duiker was observed so affected that it could be picked up with hardly any attempt to escape. To discover the nature of its illness if possible, it was brought into the tank-room.

Here it remained quite motion- less and seemed to be in a dying condition. As it was thought that it might be revived in its natural element, it was placed in one of the larger tanks, which contained a number of fish, chiefly Dasjes, Harders and Sardines.

Immediately the bird seemed to recover, and, to our astonishment, attacked the fish with the greatest vigour. By means of its webbed feet it was able to swim at a rapid rate, turning and changing its course with the greatest facility, apparently by the aid of its wings. The long neck was evidently of great utihty in seizing the fish when within striking distance. It managed to capture several before it could be removed, which was done before much damage could be effected.

It may be that such birds are in reality suffering from hunger. See observation on Duikers dying off, P-I3 - The Duikers seem capable of concerted action in their fishing operations, and I am informed by Mr. Daneel, a member of the Fishery Board, that he has seen them surrounding a shoal of fish, rounding them up like a flock of sheep, in which crowded condition they could be more easily captured.

They certainly seem to endeavour to drive the fish into shallow water, where they can be more easily secured. Thus at Knysna it has been observed Henkel that the birds form into wide circles, drive the fish into shallow water, and cause great damage. This is also stated by the fishermen, and has been observed on several occasions near the Marine Laboratory at 13 St.

Though small Harders are frequently found in such pools, those that appeared at this time were larger and more numerous than usual, and the Bamboo-fish, which are fairly large about 12 inches , are never found normally in these places. There had been little or no change of temperature either before or after the occurrence. A very large number of sea birds, however, were fishing in crowds close inshore, and it seemed probable that the fish were driven ashore in their endeavour to escape from their pursuers.

These birds were exclusively the common Duiker, which, particularly in a strong N. Some of the Bamboo-fish and Sardines were caught and placed in the tank at the Marine Laboratory. They showed no signs of injury or illness and lived for many months afterwards in the tanks. There are, however, certain other considerations which may have some value in deciding to what an extent this destruction of fish-life takes place.

It has been observed at various times by those in charge of the guano islands that there has been an unaccountable mortahty amongst sea birds. Some time ago I was fortunate enough to have the opportunity of observing such an occurrence on " Seal Island," one of the islands situated off the coast of German S. I was informed by Mr. Muller, British Consul, stationed at Luderitzbucht, that the Duikers were dying off in large numbers on this island, and we visited it with the purpose of ascertaining the cause of such an occurrence.

In the crevices of the rocks were numbers of dead birds, chiefly young, and here and there were others in a dying condition. The bodies of both dead and dying were in an emaciated condition, but there was no evidence of any disease. At a later date I was informed by Mr.

Muller that it had been found that the cause of the mor- tality was the great scarcity of fish, which was known to have occurred at this time. It is not unlikely that similar occur- rences observed on other islands on the West coast are due to this cause.

While the scarcity of fish may not have been due to the excessive increase of these sea birds, it is obvious that such an increase, which could bring about a marked decrease of fish, would react in such a way as to bring the number of sea birds back to their normal numbers. In other words, the [C. We will adduce evidence later on to show that the scarcity of fish in this case was probably not due to the increase of the sea birds, but the occurrence seems to indicate that scarcity of fish would be as fatal to the existence of the sea birds as to the fishing industry and would result in their own destruction.

Amongst birds, penguins appear to be more prone to disease than any other kind. We have had considerable mortality among these birds from time to time, the last of which occurred between two and three years ago , when the penguins came out of the water and dropped dead in large numbers. The excessive increase of Seals is another alleged cause of a diminishing fish supply, and fishermen complain of this, even more than of the protection and increase of sea birds. Like the guano-producing sea birds, the seals are strictly protected by Government.

A few years ago, when the seals had been protected for a number of years for a " knock down," they had increased to enormous proportions and, even yet, with a modified protection, they are very abundant some zealous, but ill-informed, people in England, who advocate the protection of wild animals, state that the Cape seal is nearly extinct. Under this system of protection, these in- telligent animals become so bold as to avail themselves of the fishing operations of the fishermen for a supply of fish.

They are especially troublesome at the Snoek season. Snoek are powerful and rapid swimmers, and are probably not easily captured by the unaided effort of the seal. When caught on the fishing line, however, they are more or less hampered, and the seals soon learn to know this and avail themselves of the opportunity to seize and devour them. The fishermen were prohibited by law from killing the seal, and the only way to get rid of it legally was to come alongside of another boat, to whicn it might then transfer its attention.

Frequently the fishermen had to come home in despair of getting rid of the unwelcome company. At Seal Island, in Mossel Bay, the fishermen state that the fish is so scarce in the vicinity of this seal-frequented rock that it is useless to attempt any fishing in its neighbourhood. Porpoises on the east coast cause considerable damage to the fish supply, and sharks everywhere do the same.

Por- poises are troublesome, particularly at Durban, and it has been found that if a few are shot and wounded they make for the open sea, taking all the others with them and there is no more trouble for some days. The escape of injurious matter from wrecks is known to have caused more or less extensive destruction of fish. The best example of this is an occurrence which took place at Knysna.

The Knysna harbour, or lagoon, is a large sheet of water, much smaller than Saldanha Bay, but, like it, shut off from the sea except for a comparatively narrow opening. On one occasion a ship, containing creosote for the sleeper factory there, was wrecked, and the oily substance escaped, spreading out on the surface of the lagoon.

The effect was very marked, nearly all the living animals in the water being killed off. An undoubted cause of the destruction of fish is the presence of fresh water in tidal rivers and lagoons. For in- stance, in October, , a sudden and great fall of rain oc- curred after a period of drought in the Eastern Province and the whole of the sea water in the Zwartkops River, from the ebb and flow to the mouth a distance of about six miles was driven out to sea.

After the subsidence of the water, many dead sea fish were found, and a large number of Cuttlefish, which live in the grassy salt-water pools of the river. Such an occurrence is said to be not uncommon in this region, and has been even more marked in the case of great floods in the other rivers of the east coast.

At Knysna the fishermen expect an influx of sea fish after such an occurrence as Kabeljauw and other fish come in to devour the dead Cuttlefish. Cases of destruction of sea fish by fresh water are not unknown in other parts of the world. A curious method of stating the same fact is the apparently anomalous allegation that the decrease of fish in Soutli Africa is due to the increase of jackals, and that in the following way. Increase in the number of jackals necessitates the protection of sheep in a kraal during the night.

The constant passing of the sheep to and from the kraal causes the gradual formation of more or less well-trodden paths ; by these paths the surface water flows off more quickly, deepening them, so that deep sluits are ultimately formed ; by these, the water, instead of soaking down into the surface of the ground, flows away quickly into the rivers, which are thus, in heavy rains, flooded [C. The argument reminds one of the more famihar story of old maids and clov-er crops : Increase of old maids means increase of cats, which brings about decrease of mice ; decrease of mice means increase of bees, on which they feed, and increased number of bees ensures better fertihsation of the clover plant.

Such great floods, however, are not very frequent occur- rences, and cannot be the cause of any great diminution in the fish supply generally. Some 25 years ago an American schooner, the Alice, visited the Cape especially equipped with purse-seine nets for the capture chiefly of Mackerel, for which there was a great demand in America. The nets proved very effective, not only Mackerel but many kinds of fish being caught in very large numbers.

As Mackerel only were wanted, the other fish were practically given away. The catching of such numbers of fish, by means of this kind of net, which was entirely new to the native fishermen, aroused suspicion that the method adopted was injurious to the fishing industry, and the fisher- men made representations to the Government that the fish supply was being seriously affected.

There being no inde- pendent evidence available that the fish supply was not diminishing, nor that the operation of the American nets were not the cause of the alleged diminution, a law was passed in repealed in restricting the size of nets in such a way as to render it impossible to use the new net. The development of the traivliiig industry was at one time jeopardised by allegations that diminution of the fish supply had followed the introduction of this method of fishing.

As a result of the survey of the Government trawler the Pieter Faure large areas were found suitable for trawling. At the outset of this experiment the results did not seem promising, and no opposition was aroused. One native fisherman, indeed, undertook to " eat all the fish the Pieter Faure could catch.

The supply of fish, it was stated, was falling off as a result of the trawling, and serious damage was being done to the " spawn " of the fish, which lay on the sea bottom, over which the trawl net was dragged. Representa- tions were made to Parliament, and so serious did the matter seem that a Select Committee was appointed to enquire into the allegations.

Fortunately a system of fishery statistics had been instituted, and investigations into the spawning 17 habits of the fish had been carried out at the Government Marine Laboratory. On reference to the statistics, no diminu- tion in the supply was observed, and the work at the Marine Station clearly showed that the fish, whose spawn was said to be destroyed, had eggs and larvae, which floated at the surface of the sea.

The decision of the Committee was that the allegations were not substantiated, and they recommended the continuation of the exploratory work. This regulation had in view chiefly the protection of the Harder Mullet caught by means of seine nets. From recent investigation it would appear that this mesh is still too small to allow the escape of the immature fish. The capture of small fish by lines as well as by net is also suspected to be a source of danger to the fish supply.

Red water is a phenomenon observed not infrequently in South African seas. It consists of masses of red-coloured water sometimes a mile or two in extent, at other times occurring only in small patches. In False Bay it may be seen, usually several times during the summer months, and presents a very remarkable appearance, being frequently of an almost blood-red colour.

It consists of multitudes of NoctilucUf normally present in sea water nearly everywhere. At certain times, however, they increase enormously in numbers, when they can be seen to consist of the minute egg-like bodies, which in mass present the conspicuous red colour referred to.

Such crowding together of these minute organisms appears to pollute the water, for when examined microscopically most were found to be dead. It has been observed that fish seem to avoid the red water, and fishermen do not care to fish in its vicinity. It is said that Mullet caught in it, decay very quickly, becoming quite decomposed if left ungutted overnight.

One or two instances are known in which fish and other marine animals have been killed apparently by such polluting of the water. I am indebted to an old resident in Saldanha Bay for some particulars of such an occurrence at that place.

He stated that on one occasion, the only one in his experience, about the [C. The fish in the bay were seen floating belly upwards in a disabled condition. Some of them were cast on shore in quantities at the end of the bay, in such numbers that they were " taken away in cartloads. The fish were found swimming, head above water, apparently in a stupefied condition. They filled their boat. These fish were found in dark red water. Many persons were taken ill, and I believe some died after eating fish, especially shell fish.

I myself saw several baboons lying dead on the beach near Simon's Town with clam shells in their paws. The last observation is, however, probably quite apart from the occur- rence of " phosphorus " in Table Bay. The baboons may have been poisoned by eating the " white mussel " [Donax serra , which at certain seasons appears to be poisonous.

Another somewhat analogous occurrence is frequently observed on the West coast. This is the presence of what is known among the fishermen there as " dark water. At other times they seldom do so without some visible signs of the fish, though they occasionally make such " blind treks " at night when fish are scarce. The presence of these minute forms of vegetable life in the open seas, as is well known, tends to keep the water pure and favourable for 19 animal life, on account of the oxygen which is given off ; they are indeed probably the basis of the food supply for fish and all other animals in the ocean.

Their presence in quantity, therefore would have the effect of attracting the fish, especially such fish as Mullet and Sardine, which again would be followed by the larger fish, which prey upon them. It would seem, however, that in some circumstances, the presence of large quantities of vegetable matter in the sea may lead to organic decay and the suft'ocation of fish, as in the case of " red water.

M'Lachlan, a resident of many years' experience in the fishing industry at Stumpnose Bay, seems to bear on this point. After narrating the case in which fish were found in " red water," he continues : " At another time I saw hundreds of large Steenbras fish, floating with their heads above water in a similar manner. The fishermen landed lots of them. I went afloat with a small boat, and to my surprise saw numerous Klip-fish and Hottentot-fish floating about in a stupefied condition. At the same time our fishermen picked up large quantities of Galjoen-fish on the beach at Schell Bay.

In this instance, the water where the fish were found looked a thick greenish colour, with small particles of matter resem- bling a kind of mica. The night previous there had been a thunderstorm. My opinion was that very probably a thunderbolt had burst into the sea during the night, thus causing the fish to be stunned. That masses of diatoms do decay in such a manner on the West coast will appear very probable from the incident related as occurring at Walfish Bay.

Under this last heading are included a number of very striking cases of destruction of fish attributed often to sub- marine disturbances, cold currents, etc. They seem to indicate a possible explanation of cases of general decrease in the fish supply in South Africa and are dealt with in detail.

The most striking instances of this are recorded from the west coast, in and near Walfish Bay. The first case on record is an occurrence which took place at Swakopmund, a comparatively exposed seaport in German territory, a little to the north of the excellent and sheltered harbour of Walfish Bay.

The following [C. It was from Mr. Koch to Mr. Bam, and was kindly handed to me by Prof. These Mussels had not been seen before nor were they ever found subsequently. On the evening of the 20th December, , some native fishermen procured eels, which were unknown. On the following morning these were again found, and other fish were seen, the natives, however, fearing to make use of them on account of the peculiar colour of the water.

At nine o'clock of the same day, it being spring tide, Mrs. Koch, along with the wife of Mr. Bauman, the missionary, visited the beach and saw hundreds of living and struggling " zappelende " fish cast up on the sand by each wave. They were of all sizes and kinds, and included large Dog-fish. This continued for three days ; the fish lay as far up as the sand dunes, a half to three quarters of an hour's walk behind the houses there is a wide stretch of level ground, occasionally inundated by high tide, between the houses at Walfish Bay and the sand dunes, situated some distance further inland , and were heaped to a height of one or two feet.

On Christmas eve it was almost impossible to proceed to the church on account of the odour, and it was scarcely possible to walk about without stepping on the dead fish, which lay between the houses close up to the doors. The stench became so great that it would undoubtedly have caused illness had it not been for the South-west wind, which springs up almost every afternoon.

It was useless to think of attempting to bury those millions of fish. Some English and Swedes attempted this in the case of the larger fish, but the fish, specially Harders, continued to be cast up anew. Everything of a white colour became black, even the deck houses of the Lewis Alfred, which had returned after three weeks to dis- charge her cargo. The odour of the dead fish had been felt on board at Usapf.

After a few months the skeletons on the shore in the neighbourhood of the lagoon formed a pile five to six feet in height. Then began a plague of flies. Bam remarks with reference to the colour of the water : " When I saw it it was inky, and must have been much darker in hueiprevious to my visit, which was several months after the occurrence.

We felt ill the whole day on account of the smell, and it is surprising that it could have been endured for six months. It was only in September that it became bearable. In the fish lay 20 to 30 minutes' walk behind the houses as far as the spring tides usually rise, and in only to just behind the houses. Koch adds to his wife's narrative that no explanation of this occurrence was found till a few months previous to his time of writing 23rd September, , when there appeared, near Pelican Point, a small island, about nine feet above the Gurface of the water.

He describes it as a shapeless "un- fertige " mass smelling strongly of sulphuretted hydrogen. There was at the time, he adds, a specially strong outburst of gas which killed off the fish far round about. The occurrence referred to is described in some detail by Mr. Waldron Tr. Africa, vol. This casting up of the terrified and dying fish continued for about three days, and the stench arising from the decaying mass was terrible. I was told that some of the poor blacks ate of the dead fish, and many died with excruciating agonies therefrom.

Perhaps the wholesale casting up of dead whales may account for the great number of whale bones to be seen so frequently on the littoral of Table and False Bays, used as gate posts, fences or beacons. I throw out this suggestion for the consideration of the curious in such matters. A number were observed by the lighthouse-keeper in the water in a " sick " condition.

They seemed helpless and many of them were washed ashore. This [C. Nothing particularly striking as to the state of the weather or sea was observed at the time. On further enquiry at Port Elizabeth, confirmation of the occurrence was procured, and the lighthouse-keeper then stationed at Cape Receife was good enough to furnish the following entry from the log kept there : " i6th December, Large quantity of fish and sharks washed up on the beach, mostly alive when washed up, but soon die.

The fish are of various kinds, but mostly Barbers and a fish with a peculiar beak like a parrot. Dentex argyrozona is not a shallow-water form, but as it is mentioned only from memory and after an interval of 18 years, there may have been an error here. Another case is recorded from East London. On the 26th September, , a paragraph appeared in the Peninsula Herald stating that " tons upon tons of dead fish have lately been cast up upon the East London beach, varying in weight from 3 to 60 lbs.

The coast was strewn with them from Christmas Vale to the Keiskama Mouth. Smith, Secretary of the Harbour Board, Durban, wrote : " We heard of the strange occurrence to which you refer, but as far as I am able to learn and I have caused special enquiries to be made , nothing of a like nature has been seen on our coast.

We have occasionally large numbers of Shad and Salmon thrown up, but that is the work of the porpoises and instead of being dead and limp and starved, they are very much alive and make an acceptable addition to the fishmonger's slab. One such instance occurred in the river Nahoon , when a Kafir boy simply took the fish out of the river from off the bank.

Upon cleaning it the intestines were found quite empty. It was, however, cooked and eaten by a family near by. Unfortunately, I have not any reliable information as to the species of fish seen on the beach, mostly to the westward of Cove Rock, simply a general statement saying ' all sorts of fish. Such fish when examined have been invariably found to have empty stomachs.

I do not think that the fish thrown away by the trawlers, as some allege, would account for such large quan- tities as those on the beach, and when similar occurrences took place earlier in the 25 years period there were no trawlers. Wood, of East London, took some pains to ascertain the facts of the case. He writes : " I have met a Keiskama North resident, who saw the fish on the beach — those which were those probably alluded to in the newspaper paragraph you quote.

As well as I can gather, the report first appeared in the Daily Despatch here, and came from a correspondent out Keiskama way. I am told it did not state fish had been cast up on the East London beach, and as far as I have learned nothing of the kind was noticed here. According to my Keiskama informant, sometime about the middle of September, hearing from a Kafir that there was a lot of fish lying about the beach, he took a few sacks and set out to collect the gifts the gods had sent.

He found them by the score, a few hundreds altogether upon the mile or so of beach and, with the exception of a few here and there, they were more or less alive. Upon the sand washed by the surf they were lying about in a limp exhausted sort of condition, whilst in the rock pools they moved about as if dazed. There had been a heavy swell on for some days, but the water was warm. His young brother, who did the wading, said that it was quite nice and warm. This condition would correspond with what is stated in en- closed letter from one of the skippers of our local trawlers.

He went back to get his sacks refilled, but the tide had come up in the interval and they were never seen again. Soles were not observed. My crew drew my attention to it. The depth of the water was 24 to 32 fathoms. I may mention that the fishing on these dates was very poor. Willows reports : " The report in the Peninsula Herald is correct ; the sea, in which the dead and living fish were found in abundance, also extended east of Christmas Vale to the mouth of the Igoda River.

Several days prior to the washing up of the fish strong south-east winds prevailed, and the general opinion is that they were the direct cause. However, this is an open question, owing mainly to the fact that some of the varieties washed up are known as " deep sea fish," and, therefore, not hkely to be incapacitated by rough seas and, in addition, I noticed several eels.

For several days live fish were caught in pools at low water, after the winds had abated, and the condition of the sea was fairly smooth. This gave rise to the supposition on my part that there was a possibility of the fish and eels having eaten a variety of sea weed, that at this particular time had a paralysing effect, thus causing them to lose control and be washed up by the force of the waves.

The fish were eaten by natives and others without any ill effects About two and a-half years ago a similar occuirence took place along the beach in the vicinity of the Igulu River mouth. Holdstock reports : " The fish were alive when washed up on the beach, as some were caught alive in shallow water. My opinion is that the fish were blinded with sand, which had been dispatched? I have not heard of any ashore to the east of East London. Regnart, of Jeffrey's Bay, writes : " Up to the present 23rd October, there have been no signs of fish being dead or paralysed on this coast.

For the last three months a very strong current has been running to the west ; fish are plentiful, but will not feed. I beheve I notified to your office in December last of a number of Kantonkel being washed out, some dead and others numbed with the cold. The water had been so cold for some days previously that it was impossible to bathe. On the 23rd most of the fish were washed ashore ; they were of large size, but only of the one kind.

I go myself occasionally with the boats and should have noticed and reported anything exceptional. William Jones, acting Port Officer at Plettenberg Bay, writes : " After diligent enquiry and search along the sea coast of the bay I have come to the conclusion that the mortality among the fish has not reached this bay. May not the marine eruption reported for the week ended 26th ultimo have some connection with the death of so many fish.

Whilst the up- heaval of the sea lasted it was awfully grand and those looking at it were relieved when it subsided as a boiling crater. It subsided exactly in the same place, showing great commo- tion in the sea, similar to volcanic eruption. Donald Ben at Knysna Heads reported that " there were a few dead fish washed up on the beach in the early part of last month September, , but not sufficient to send a report on.

The names of the fish washed up were Pruns- kopp of 60 to 80 lbs ; Dageraad, 3 to 10 lbs. I have known these kinds of fish to die more or less every year from cold water, which is caused by a cold southerly current setting inshore with south-east winds.

This cold current has no effect on deep-sea fish, only on rock fish. McNaughton, Conservator of Forests, Knysna, reports : " It is no uncommon occurrence for fish to be washed up along the coast in an apparently dead condition. To a greater or lesser extent it happens annually. To my knowledge it has occurred periodically for the last fourteen years The fish if uninjured on the rocks are apparently quite healthy and recover their vitality in warm sheltered pools.

The usual time of the year for the occurrence is late autumn February- March after heavy south-east gales. Some years ago the mortality was excessive, and this was accounted for by the fact that the south-east gales may have driven an iceberg to within a comparatively short distance from these shores, with the result that the water temperature was abnormal. The area affected, to my knowledge, is from Cape St. Francis to Cape St. Wadner, manager of the fishing company there, that " last week the bottom of the sea was covered with dead and rotten fish, and at times the net was quite full of these.

When the bag was opened and the fish fell on deck, the stench was abominable, and the skipper and the men handling the net felt so sick that they had to throw up [C. In some instances only some of the big fish were found in the net.

Dead fish are also floating about in the sea and the bay. Wadner adds that " the cause of this extraordinary occurrence is difficult to tell. A cold mist has enveloped the bay and extended far out to sea on several occasions lately. I am told that that indicates icebergs not far away, and I should not wonder if a cold current originating from these has killed off a number of fish and driven the remainder to find warmer waters.

Strange enough, the soles do not seem to suffer, but it may be that the current has swept above them. McFarlane, at Hermanus, reported that " no dead fish have ever been cast up on our shores, nor have we seen dead fish floating about here at any time. Avenell, of Somerset Strand, reported that no such occurrence was known at that place.

No fish was reported to have been cast up on the beach either at False Bay or Table Bay at this time. Anderson, at Hoetjes Bay, writes : " No dead fish were cast up on our shore during September, but such a thing has happened previously, and I think the cause must have been at that time phosphorus water, a red thick water. The Fishery Officer at Steenberg's Cove states that " no dead fish were cast up on this part of the coast during September nor has there been since " i8th February, The Fishery Officer at Paternoster also states that nothing was known of such an occurrence, and adds " this is a thing quite new to us.

Long ago some few hundred Harders Mullet washed up on our beach ; since then nothing of the kind has occurred. M'Lachlan, at Stumpnose Bay, also states 23rd Febru- ary, that nothing of the kind occurred there lately. After giving the two instances already mentioned he proceeds to state : — " Another instance was brought to my notice on the 20th March, , by the local fishermen. While out snoeking about four miles off Schell Bay reef, they came across tons of dead Sardines floating in the sea, and hundreds of dead Sea Duikers were seen floating about at the same time.

There were two currents that met together extending north and south. On the western side the water was blue, and on the eastern side the water was of a thick muddy colour, in which the dead Sardines were drifting, and my opinion is that when the sea water at some places becomes in such a morbid state, 27 it will cause the above results to all fish at the time confined to such waters.

Stigling, of Lambert's Bay, reported that " no dead fish of any description has been washed up here. On the morning of the 7th, I was informed by Mr. Henkel that, while fishing the previous night, he noticed when renewing his bait that it felt very cold, and that the water had turned suddenly cold. His companions also noticed the strik- ing fact. The fish ceased to bite, and only one Dogfish was caught subsequently. In the morning they were informed that a large fish a " Blauer " — Chrysophrys sp.

A series of temperature observations were taken on the same morning from near the village of Knysna to the " heads," where the lagoon opens by a somewhat narrow channel to the sea. At this point it was then observed that the lagoon was occupied with bodies of water of strikinglv different appearance, and sharply marked off from each other. One was of dark blue, the other of slightly pale muddy, greenish colour. The fisherman in charge of the boat said that the former was warm water and the latter was cold, and was quite familiar with the condition.

This was found to be the case. A number of seagulls were observed at one place and the fishermen said we would probably find some dead or dying fish here. One was at last seen floating belly upwards in the water and moving its fins slowly as if in a stupefied condi- tion. On being touched it struggled and dived into the water only, however, to come up again shortly.

The return journey was made by the main channel sometime after the tide had turned, setting in strongly into the lagoon, and the following [C. From the signal-station at the Heads the cold water recognised by its colour could be seen, stretching along the shore in both directions as far as the eye could reach, while, at about a distance of two or three miles out to sea, the warm water blue could be seen with the same sharp line of distinction between them as observed in the lagoon.

The signalman had noted the occurrence of the cold water and, on visiting the beach on Saturday, had observed " thousands of dead fish. The signalman further stated that such occurrences were frequent in January and February, and the dead fish could easily be seen at sea from his look-out, and that the cold water appeared as a muddy-looking band, stretch- ing along the shore, as in the present instance.

It appeared generally after a continuous or strong south-east wind, which he states blows along the shore, but is more associated with the direction of the inshore current ; this, he says, is usually from west to east, but, with cold water, it is reversed and flows to the west.

This westerly current is usually associated with south-east winds, but not always, as he has observed occasion- ally a strong westerly current of cold water with no accom- panving south-east wind. The species not affected include Kabeljaauw, Bontrok, Seventy-four here called silver fish , Galjoen, Harder, etc.

Sciaena hololepidota, Sargus cervinus, Dentex undulatus, Dipterodon capensis, Mugil spp. Whatever the origin of the cold water may be, it apparently comes up from the lower or deeper regions of the sea, and would thus cut off the rock and shore-frequenting 29 forms, which are mostly bottom feeders, while the surface- frequenting forms would be able to resort to the warmer surface water.

The presence of patches of warm blue water in the river is apparently due to some of this normal sea water being cut off by the upwelling of the colder water along the shore. It has been observed further that, to escape the cold water, the shore forms come crowding into the lagoon, and seek out the warmer and shallow waters. That this is of frequent occurrence is shown by the fact that the fishermen find the best catches in these places during the presence of the cold water.

The continuance of the cold inset would, of course, thus lead to a still greater mortality in the lagoon and, a few years ago, many fish were washed ashore dead and heaped up in great numbers on the banks of the lagoon. The following notes on a case of extensive destruction of fish at the " Kommetje," a small basin to the south of Hout Bay, were taken at the time of the occurrence. Runciman, M. It showed no signs of disease and was in excellent condition.

On visiting the locality, undoubted evidence was found that there had been extensive mortality among the fish. The report of the occurrence had reached neighbouring farms and villages, and the beach was being diligently searched by coloured people for further spoils. One farmer testified that he had seen some dead though fresh fish on Tuesday night, others being alive and floundering in the water in a dazed condition ; one large Galjoen he caught with difiiculty swimming about in the water.

He stated that many more fish were found on the following day, a few at a wreck but most on the " long beach " near Klein Slangkop, a mile or so from the wreck. All the witnesses were of opinion that the death of fish was due to the escape of some injurious matter from this wreck. The ship had come ashore immediately before the occurrence and was laden with general merchandise, including dynamite, cyanide, gun-cotton, soap, etc.

All the dynamite was safely taken off, and there had been no explosion, which might have accounted for the dead fish. The beach in the neighbourhood of the wreck was strewn to some extent with pieces of soap and gun-cotton. One fisherman was certain that the injury to the fish had been caused by their eating the soap, the effects of which he alleged were to stupefy them temporarily. He said he had found pieces of soap and gun-cotton inside the dead [C.

The stomach of a Galjoen I examined contained no soap or gun-cotton, and the pieces of soap seen had no marks on them which might not have been caused by dashing against the rocks. This same fisherman, who fives near the beach, had first seen some dead fish on Monday afternoon, but most on Wednesday, when three or four cartloads each of about to fish were taken from the beach, there being about a thousand fish in all.

They were mostly bought by Jewish fishmongers and sold in Cape Town, and no injurious effects were reported from the con- sumers. The fisherman himself had eaten them without any ill effect. No great change had been observed in the temperature of the sea at St. James in False Bay, at or near this time in observations taken three times a day. In attempting to co-ordinate these various observations and to discover some cause or causes of such occurrences many difficulties arise.

Some narratives are set down from memory several years after the event, and many may be influenced by preconceived ideas as to the causes of the pheno- mena. On the whole, however, they are so circumstantial, and deal with such well-marked incidents, that they them- selves are well worthy of permanent record, and, maybe, are of more value in this enquiry than any deductions which may at this stage be drawn from them.

They point to certain biological and physical characteristics of the South African seas which require further investigation on account of their practical as well as their purely scientific importance. We may in the first place eliminate most of the alleged causes of the diminutions of the fish supply mentioned in the previous sections as insufficient at least to account for any such sudden and wholesale destruction of marine life as is described in the preceding instances.

We may further narrow the enquiry by considering first those cases in which "red water" appears. The most definite instance of this is that occurring 31 in Saldanha Bay about the year and near Stumpnose Bay about To this category may also be added the case of the " phosphorus " in Table Bay about In the occur- rence at Swakopmund in the peculiar red " bliitig" colour of the sea would seem to indicate that there was at least some element of this nature present here, though it is to be noted that the colour of the water was described by another observer- some months after the occurrence as " inky.

There seems, however, to be no doubt that in some instance decaying masses of Noctiluca " red water " is the immediate cause of the death of fish by suffocation, though there re- mains to be accounted for the cause of the accumulation and dying-off of these animals. The second apparent cause of such phenomena is the pre- sence of vegetable matter diatoms in masses, leading to decomposition and consequent suffocation of sea animals. This appears to have happened in the occurrence at Schell Bay.

The main factor in the occurrences at Walfish Bay also seems to have been the decay of diatomaceous matter in the bottom of the bay in enormous quantities, a sample of the mud at the bottom of the bay having been found on microscopic examination to consist almost exclusively of diatoms. The occurrence at Knysna will not, however, admit of any such explanations. There is no record of the presence of Noctiluca in large quantities either in the sea or the lagoon.

Here their absence in quantity may be accounted for by the fact that there is here no chance of the water remaining in an undisturbed state, as the currents in the sea are strong and the entrance to the lagoon is very narrow. Special enquiries were made as to whether " red water " was ever found in the lagoon, and it appears to be unknown. The explanation generally accepted at Knysna is that the death of fish is due to cold water, as it is always associated with the presence of such water.

The occurrence is annual, and in a more or less marked degree, so that it may be accepted as a statement of fact that the fish die off when the cold water appears — whether from the actual cold or not is a different question. Further, it is observed on such occasions that the cold water is of a distinctly different colour from that of th normal sea water, so marked that ordinary fishermen recognis it readily and expect to find dying or dead fish in it.

The fishermen describe the cold water as of a muddy colour. The actual colour of the cold water is a pale muddy or sandy colour with a tinge of green, though, when dipped up in a vessel, it is seen to be much more transparent than the blue water. The muddy and blue water, described by Mr. M'Lachlan at Stumpnose Bay, on the west coast, agrees with the condition at Knysna, and here also dead fish Sardines " in tons " were found in the muddy water.

It is not mentioned, however, that the muddy water was particularly cold, and the presence of hundreds of dead sea Duikers is a puzzling element. It cannot be readily sup- posed that these birds died of cold, nor can it be imagined that they died of hunger in the presence of so many dead fish. The only explanation that would seem to fit in with the other factors, is that they died in some way from eating the dead fish, for which however there is no evidence.

Other cases in which the coldness of the water seems to have played a part are those near East London, 26th September, , and at Mossel Bay at about the same time shortly before the 2oth. On the other hand, we have the evidence of the trawler that, on the 8th to the nth, while trawling 18 miles east of East London, the water was so warm that it attracted special attention.

This would, of course, be at some distance from the shore, so that, while the cold water was inshore, the water further to sea was warm. The presence of warm water in the pools at Keiskama may have been due to the shallowness of the water and its heating up after the occurrence.

Tempera- tures were also observed at Port St. In the occurrence at Mossel Bay the presence of a " cold mist envelop- ing the Bay " was adduced as evidence of the existence of cold water, " perhaps due to an iceberg. In the Table Bay case and Cape Receife there is no mention of cold water, nor of any peculiarity in the colour of the water. The coastline affected is of particular interest. Such occurrences do not seem to be known in Natal, and are con- lined, so far as records go, to the coast extending from East 23 London on the east coast round the south coast to Walfisli Bay or Swakopmund on the west coast.

It is of special interest also to note that, while at all other places the occurrence seems to be more or less intermittent, at Knysna and at Walfish Bay it is well recognised as an annual one. At both of these places it occurs also at a definite time of the year — the mid and late summer months. It is just on this coast that the cold Antarctic current going from west to east strikes the continent of Africa, and meets the warm Mozambique current coming southwards along the east coast, and it may be supposed that Knysna is a point at which forms of animal life, accustomed more or less to warmer water than is found further west, would suffer more from the inset of the cold water.

Compare the effects of cold on the Frost-fish, p. The dying off of the fish at Wallish Bay seems more attribut- able to the pollution of the water by decaying vegetable matter accumulating in the bay from the sea. The dying off of the diatoms may be due to the change of temperature which the west coast division of the Antarctic current undergoes here, just as the south coast division of the current does at Knysna It may be of significance that Soles are frequently cast up at Walfish Bay, but not at Knysna.

They were notably absent from the other occurrences. It is to be noted also that it is mainly the waters of the immediate coast that are affected, pointing to an upswelling of cold waters Antarctic current V from under the warmer waters Mozambique stream? These physical features are reflected in the forms of animal life in the sea, the fauna of the east coast being markedly different from that of the west.

The Snoek, for instance, is a charac- teristic west coast form, and occurs, at certain seasons, in great abundance from Cape Point northwards. It is found occasionally at Mossel Bay and Plettenberg Bay, but very rarely at Port Elizabeth, and has not been recorded from the east coast north of that town. It is a fish of the high seas and only at times comes close inshore. It has never been men- tioned as among the fish affected in the above cases, but it may be accepted as established that its occurrence is largely influenced directly or indirectly by the temperature of the water.

It is essentially a migratory fish, and doubtless its abundance or scarcity on the coast of South Africa is dependent to some extent at least on the temperature condition of the sea at the season in which it approaches the shore. It extends from the east coast along the south coast as far as False Bay. It is [C. Unlike the Snoek, it is a shore-frequenting form, and it is of significance that at Knysna, when cases of mortality among fish occur, it is the species most seriously affected.

These two cases illustrate the influence of the cold stream in its extent along the coast. Other cases illustrate the up- swelling of the cold water on the shores from under the warm water, as it is the shore forms which are mostly affected. There seems little doubt, therefore, not only that the present distribution of fish and marine fauna generally on the South African Coast is determined by the cold Antarctic water meet- ing the warm Agulhas current, but that the relative abundance at different times may be due to the relative strength of the opposing currents, the effect of the cold current being in severe cases an extensive mortality in marine life, the extension of the cold water for instance to the east, permitting the presence of Snoek as far east as Port Elizabeth, and the extension of the warm water permitting the presence of the Red Stumpnose towards the west even occasionally to Table Bay.

If a pelagic rather than a rock-frequenting fish be desired as an example comparable with the Snoek, Elops saurus the " springer " of Natal and " Cape Salmon " of Port Elizabeth may be cited, as it is common on the east coast and only occasionally found as far west as Knysna. The cause of the warm Mozambique current on the east coast, and its continuation as the Agulhas current on the south coast, is the trade winds of the Indian ocean, which drive the water from a south-easterly direction towards the Equator, where it becomes heated up, and, as the Equatorial current, impinges on the African continent, and is diverted along its eastern shore.

It is, therefore, on the east coast of South Africa, turned southwards and encounters the south-east trade winds in the modified form of the Cape south-easters. These have a tendency to drive it back, or, at least, keep it in check, so that the Antarctic current will extend further to the east. It seems to be due to this that we have the apparently anomalous fact that an on-shore wind S.

There are, however, many obscure points regarding the currents of the South African coast, which can only be cleared up by a series of systematic observations. A good deal might be done by observation of surface temperatures at stations on the coast line, but it is essential that observations of tem- 35 peratiire, salinity, etc. It need hardly be pointed out that the fuller information and investigation of the various factors which influence the fish supply are of urgent necessity from a purely practical point of view.

Even should it prove that some or all of these are beyond control, to which indeed some of the evidence seems to point, yet their elucidation will be of the utmost importance, if only to prevent legislation in futile or injurious directions, and may prove of a more direct use in indicating in what regions fish may or may not be expected to be found. Thus, to take a concrete example, strong and continued south-east winds may be found to be associated with the presence of the colder waters and their characteristic fish, such as the Snoek.

On the other hand, in the absence of such winds, the fish characteristic of warmer waters may more profitably be looked for. The proper control of injurious methods of fishing if proved to be injurious, the imposition of close seasons, size limits, or even protection in certain areas are therefore obviously bound up with an accurate knowledge of the physical conditions of life in the sea.

Finally, it must be recognised also that whatever the cause may be, the history of nearly all fisheries is that the fishermen have to resort to more effective methods of fishing, and that the small open boats at first in use become no longer adequate to meet requirements. Fishermen are often of a conservative disposition, and as often are unable to provide the means for such improvements. In many countries the State has come to their assistance, and by a system of judicious loans has considerably advanced the industry.

The South African native fishermen are, in these respects, no exception to fisher- men in general, and some such system may also prove of great advantage in the development of this section of the industry in this country. The improved harbour accommodation about to be provided by Government at Table Bay and Kalk Bay will render it possible for the fishermen to use larger and better equipped boats, in place of the small open boats, which have to be carried ashore out of reach of the sea on their return from fishing operations.

The present time, therefore, is suitable for the initiation of some such system. The greatest advance in the industry is of course to be looked for from independent companies, such as the trawling companies, in no need of such assistance, but there will always remain plenty of scope for the native fishermen, whose field of operation lies closer inshore [C.

Since the last account of this subject Marine Biological Report No. In the course of the enquiry, additional information has been obtained, some of which it is desirable to put on record. All the evidence pointed to the immediate necessity of adequate legislative measures for the safeguarding of the industry, and the size limit is now raised from three to four inches, four months' close season is imposed, and females in berry are protected — the only excep- tion to the size limit being a concession to the native fishermen in the case of crawfish taken solely for the purposes of bait.

It became apparent during the course of the enquiry that a good deal of information was still desirable with regard to the times of spawning, the possible migration of the fish from one part of the coast to another, the alleged difference in the spawning season at different parts of the coast, the size at which crawfish become mature, at what times and in what places the males and females were to be found, etc.

The experimental hauls of crawfish have been continued, and we have now a record of such hauls for a complete year, made in Table Bay off the Woodstock Beach. These additional observations are given here, and a summary for the whole year prepared, so that it is seen at a glance how the crawfish vary in number and kind young or old, male or female at this locality.

They throw some light on the above questions. A later stage, the " puerulus " or " natant " stage of the crawfish, has been found and some preliminary notes on this are added. The experimental rearing of crawfish has been continued at the Marine Station at St. In this connection, it is of interest to learn that the Japanese, who have a valuable crawfish industry of their own, have for some time been experimenting in the same direction.

Z7 The following notes may therefore be arranged under the headings : — 1. Information from canners and fishermen. Experimental hauls of Crawfish. Tow-nettings and larvae of Crawfish. The " puerulus," or natant stage of the Crawfish. Information on Crawfish obtained from Canning Companies and P'ishermen. Representatives of the following canning companies gave evidence at the enquiry held by the Fishery Board. Native and Italian fishermen were also represented.

Helena Bay Stephan Bros. Van Zweiberg. Helena Bay no diminution in the supply is noted, except near the coast. There are two seasons for Crawfish — October to November, when large males are caught, and April to June, when mostly females are caught. Males cast shell from about December 15th to March ist, and will not take bait then.

They hide in their holes, so that their enemies cannot get them. The female fish lie in the shallows until their eggs are nearly mature, when the males come inshore and " milk " the eggs and then go back again this appears to be mcorrect. The females, when depositing their eggs, lie among the rocks at low water. They have been caught 40 or 50 yards from the shore.

When the females are spawning, the boats do not go after them, but have to go into deeper water for their catches. They very rarely catch a female compare the statements of Table Bay fishermen on this point. With regard to evidence of migration, about the beginning of October, , the boats had to go to a place right south to the other side of North Bay, and by the middle of October the boats had got to the middle of North Bay showing a movement northwards in October.

From about the middle of February to early in July about 80 per cent, are mature males, the rest being small males of 3 to 4 inches. The mature males are more than 4 inches. From the middle of July to early in September, females and small males are found. This appears to be the season when females and the small fish are casting their shell, large quan- tities of empty shells being cast up on the beach there. From the middle of September to early in December, the fish are all large males.

Thus in one week, of , fish, 90 per cent, were more than 5 inches in length. They may grow to 8 inches. This is the best season north of Jacobs Rock. In December, as the males cast their shell, they go off into deeper water, and return in February. In tabular form, these facts may be stated as follows : — Middle of December to early in Females, 99 per cent, in berry. Males casting shell in deeper water. Middle of February to early in Males, 80 per cent, mature July. Middle of July to early in Females and small males September.

Middle of September to early Males, 90 per cent, over 5 in December. Over two million fish were used in two factories last year. In deeper water you get only large fish, in shallow water you are more likely to get small fish. At St. Martin's Point, fish measuring 8 inches are got, not five per cent, being less than 5 inches. If you come with the best bait they will not bite. We believe the close seasons, as now arranged, are very good indeed. The fish protect themselves.

Crawfish are not on a limited bank ; there are pockets of them. When the north- west wind blew at an unusual time, you would see the beach at Mouille Point covered with crawfish knocked against the rocks, because they are sick and are changing their shell.

To explore the toxicological effects of an alternative compound, namely E -1,1,4,4- tetramethyl tetrazene TMTZ , we exposed various cellular animal and human models to this compound and to the reference compound MMH. We observed no cytotoxic effects following exposure to TMTZ in animal, as well as human models. However, although the three animal models were unaffected by MMH, exposure of the human hepatic HepaRG cell model revealed that apoptotic cytotoxic effects were only detectable in proliferative human hepatic HepaRG cells and not in differentiated cells, although major biochemical modifications were uncovered in the latter.

The present findings indicate that the metabolic mechanisms of MMH toxicity is close to those described for hydrazine with numerous biochemical alterations induced by mitochondrial disruption, production of radical species, and aminotransferase inhibition. The alternative TMTZ molecule had little impact on cellular viability and proliferation of rodent and human dermic and hepatic cell models. Published by Elsevier Ltd. Hazard characterization and management of tetramethyl tin in the production of photovoltaic cell transparent conductive oxide layers.

Tetramethyl tin TMT has been used by the photovoltaics industry to prepare transparent conductive oxide films on glass. Significant health hazards, however may be associated with the use of TMT. Short-term exposures to TMT vapors in excess of accepted exposure limits can produce a range of physiological symptoms. Although less is known about the hazards from prolonged exposure to low levels of TMT, some studies suggest that effects are both cumulative and persistent.

TMT also is highly flammable and emits toxic fumes on decomposition. In an occupational setting, workers may be routinely or accidentally exposed to TMT liquids or vapors. Thermal afterburners combined with particle filtration may be used to meet these guidelines. Accidental release of the total inventory of TMT at a large-scale plant may present hazards to individuals living about 1 km from the facility's boundary.

Because of these hazards, strategies to prevent in-plant release coupled with community emergency response programs are needed. Hazardous characterization and management of tetramethyl tin in the production of photovoltaic cell transparent conductive oxide layers. Structural, spectroscopic and theoretical studies on 3,4,7,8- tetramethyl -1,phenantroline complex with picric acid.

Bator, G. The almost planar molecular complex, formed by 3,4,7,8- tetramethyl -phenantroline Me4phen and picric acid 2,4,6-trinitrophenol, PA , has been investigated by using X-ray diffraction, vibrational spectroscopy, tunnel splitting and theoretical analysis. Infra-red spectra show the hydrogen bonds are short. The number of the peaks is consistent with X-ray diffraction studies, which disclosed the inequivalence of methyl groups in the crystal structure.

The comparison of the tunnel splitting for neat Me4phen and for its complex with picric acid indicates that in the latter case the methyl groups are more strongly engaged in the intermolecular interactions, particularly with nitro group oxygen atoms of picric acid, leading to an increase of the CH3 rotational barrier height.

A novel cerium oxide nanoparticles-based colorimetric sensor using tetramethyl benzidine reagent for antioxidant activity assay. Antioxidant activity AOA assays using nanotechnology are recently developed utilizing nanoparticles of transition metal oxides, especially nanoceria that can switch between trivalent and tetravalent oxidation states of cerium.

Cerium oxide nanoparticles CeO-NPs may act as both an oxidant and an antioxidant, depending on the preparation method and particle size. Antioxidants decreased the color intensity of the nanoceria suspension, and were indirectly determined by absorbance difference. Detection limits, linearity, additivity and precision were calculated, e. The trolox equivalent antioxidant capacities of hydrophilic and lipophilic antioxidants were compatible with those of conventional antioxidant assays.

Potential interferents such as glucose, citric acid, mannitol, sorbitol and benzoic acid did not adversely affect AOA determination. The developed sensor is more sensitive and selective than similar colorimetric sensors relying on the intrinsic color change of nanoceria.

The measurement wavelength is sufficiently red-shifted, preventing possible interferences from plant pigments. Bioinspired, cysteamine-catalyzed co-silicification of 1H, 1H, 2H, 2HPerfluorooctyl triethoxysilane and tetraethyl orthosilicate : formation of superhydrophobic surfaces. Bioinspired silicification attracts a great deal of interest because of its physiologically relevant, mild conditions for hydrolysis and condensation of silica precursors, which makes the bioinspired approach superior to the conventional sol—gel process, particularly when dealing with biological entities.

However, the morphological control of silica structures with incorporation of functional groups in the bioinspired silicilication has been unexplored. In this work, we co-silicificated 1H, 1H, 2H, 2H-perfluorooctyl triethoxysilane and tetraethyl orthosilicate to investigate the morphological evolution of fluorinated silica structures in the cetyltrimethylammonium bromide-mediated, cysteamine-catalyzed silicification.

The generated micrometer-long wormlike and spherical silica structures display superhydrophobicity after film formation. Interestingly, the measurement of dynamic water contact angles shows that the morphological difference leads to a different wetting state, either the self-cleaning or the pinning state of the superhydrophobic surface. Transparent 1 T-MoS 2 nanofilm robustly anchored on substrate by layer-by-layer self-assembly and its ultra-high cycling stability as supercapacitors.

Two-dimensional MoS2 materials have attracted more and more interest and been applied to the field of energy storage because of its unique physical, optical, electronic and electrochemical properties. However, there are no reports on high-stable transparent MoS2 nanofilms as supercapacitors electrode.

The synthesis of strained polycyclic systems from readily available precursors with a minimum number of steps and with regio- and stereochemical control constitutes an important synthetic challenge. The developed chemistry has been applied to the total syntheses of 4-epi-presilphiperfolanol and 7-epi-presilphiperfolanol. Synthesis and photoluminescence of EuII in barium zinc orthosilicate : a novel green color emitting phosphor for white-LEDs.

Accumulation of radiation defects and products of radiolysis in lithium orthosilicate pebbles with silicon dioxide additions under action of high absorbed doses and high temperature in air and inert atmosphere. One of the technological problems of a fusion reactor is the change in composition and structure of ceramic breeders Li4SiO4 or Li2TiO3 pebbles during long-term operation. In this study changes in the composition and microstructure of Li4SiO4 pebbles with 2.

Three types of pebbles with different diameters and grain sizes were investigated. SEM was used to investigate structure of pebbles. It has been suggested that changes of radiation stability of lithium orthosilicate pebbles in air atmosphere comparing with irradiated pebbles in argon atmosphere is effect of chemical reaction of lithium orthosilicate surface with air containing - H2O and CO2 in irradiation process.

As well as it has been suggested that silicon dioxide - lithium metasilicate admixtures do not affect formation mechanism of radiation defect and products of radiolysis in lithium orthosilicate pebbles. Formation and accumulation of radiation-induced defects and radiolysis products in modified lithium orthosilicate pebbles with additions of titanium dioxide. Lithium orthosilicate Li4SiO4 pebbles with 2.

Therefore, it has been suggested to change the chemical composition of the reference Li4SiO4 pebbles and to add titanium dioxide TiO2 , to obtain lithium metatitanate Li2TiO3 as a second phase. The aim of this research was to investigate the formation and accumulation of radiation-induced defects RD and radiolysis products RP in the modified Li4SiO4 pebbles with different contents of TiO2 for the first time, in order to estimate and compare radiation stability.

On the basis of the obtained results, it is concluded that the modified Li4SiO4 pebbles with TiO2 additions have comparable radiation stability with the reference pebbles. N 4 -[B- 4,4,5,5- tetramethyl -1,3,2-dioxaborolan methyl]-2'-deoxycytidine as a potential boron delivery agent with respect to glioblastoma. Glioblastoma multiforme GBM is a central nervous system tumor of grade IV, according to the WHO classification, extremely resistant to all currently used forms of therapy, including resection, radiotherapy, chemotherapy or combined therapy.

Therefore, more effective treatment strategies of this tumor are needed, with boron neutron capture therapy BNCT being a potential solution, provided a proper cancer cells-targeted 10B delivery agent is found. In search of such an agent, toxicity and capacity to target DNA of a boronated derivative of 2'-deoxycytidine, N 4 -[B- 4,4,5,5- tetramethyl -1,3,2-dioxaborolan methyl]-2'-deoxycytidine 1 , was tested against human tumor vs.

The present in vitro results revealed 1 to show low toxicity for human U MG glioma cells in the mM range and even by - fold lower against normal human fibroblasts. Although demonstrated to be susceptible to phosphorylation by human deoxycytidine kinase and to undergo incorporation in cellular DNA, the boron analogue did not disturb cell proliferation when applied at non-toxic concentrations and showed low toxicity to a model metazoan organism, Caenorhabditis elegans.

Thus, N 4 -[B- 4,4,5,5- tetramethyl -1,3,2-dioxaborolan methyl]-2'-deoxycytidine appears a promising candidate for a 10B delivery agent to be used in BNCT, with C. Carbon-carbon bond activation of 2,2,6,6- tetramethyl -piperidineoxyl by a Rh II metalloradical: a combined experimental and theoretical study. An alternative ionic pathway, with a somewhat higher barrier, was identified along the closed-shell singlet surface.

Although the calculated barrier of the open-shell radical pathway is somewhat lower than the barrier for the ionic pathway, R-DFT and U-DFT are not likely comparatively accurate enough to reliably distinguish between these.

In vivo EPR imaging of differential tumor targeting using cis-3,4-di acetoxymethoxycarbonyl -2,2,5,5- tetramethyl pyrrolidinyloxyl. PubMed Central. Redler, Gage; Barth, Eugene D. Purpose EPR spectroscopy promises quantitative images of important physiologic markers of animal tumors and normal tissues, such as pO2, pH, and thiol redox status. These parameters of tissue function are conveniently reported by tailored nitroxides.

For defining tumor physiology, it is vital that nitroxides are selectively localized in tumors relative to normal tissue. Furthermore, these paramagnetic species should be specifically taken up by cells of the tumor, thereby reporting on both the site of tumor formation and the physiological status of the tissue. This study investigates the tumor localization of the novel nitroxide, cis-3,4-di acetoxymethoxycarbonyl -2,2,5,5- tetramethyl pyrrolidinyloxyl 3 relative to the corresponding di-acid 4.

Methods We obtained images of nitroxide 3 infused intravenously into C3H mice bearing 0. Results The ratio of spectral intensity from within the tumor-bearing region to that of normal tissue was higher in the mice injected with 3 relative to 4. Conclusion This establishes the possibility of tumor imaging with a nitroxide with intracellular distribution and provides the basis for EPR images of animal models to investigate the relationship between crucial aspects of tumor microenvironment and malignancy and its response to therapy.

Separation of tricyclic antidepressants by capillary zone electrophoresis with N,N,N',N'- tetramethyl -1,3-butanediamine TMBD as an effective electrolyte additive. Five tricyclic antidepressants TADs , desipramyne, nortriptyline, imipramine, doxepin and amitriptyline, were separated by using the N,N,N',N'- tetramethyl -1,3-butanediamine TMBD as additive in the background electrolyte solution. Because the tricyclic antidepressants are similar in structure, mass and pka values, their separation, by capillary zone electrophoresis, requires the careful manipulation of parameters, such as the pH and the composition of the electrolyte solution.

As basic drugs, the TADs interact with the silanol groups on the capillary wall giving rise to peak broadening and asymmetry, non reproducible migration times and failing in selectivity. At this pH the separation was not possible without additive. This result is due to the reduced electroosmotic flow whose mobility is at a value of 10 -9 m 2 V -1 s Extrapolation of experimental vapor-phase C-H J-couplings to a zero-pressure limit permitted determining the 1 J 0,CH s in methyl groups of their nearly isolated molecules.

A very good agreement theory vs. Etudes optiques de nouveaux materiaux laser: Des orthosilicates dopes a l'ytterbium: Le yttrium lutetium,scandium pentoxide de silicium. La decouverte et l'elaboration de nouveaux materiaux laser solides suscitent beaucoup d'interet parmi la communaute scientifique. En particulier les lasers dans la gamme de frequence du micron debouchent sur beaucoup d'applications, en telecommunication, en medecine, dans le domaine militaire, pour la, decoupe des metaux lasers de puissance , en optique non lineaire doublage de frequence, bistabilite optique.

Le plus couramment utilise actuellement est le Nd:YAG dans cette famille de laser, mais des remplacants plus performants sont toujours recherches. Parmi les matrices cristallines pouvant accueillir l'ytterbium, les orthosilicates Yb:Y 2SiO5, Yb:Lu2SiO5 et Yb:Sc2SiO 5 se positionnent tres bien, du fait de leur bonne conductivite thermique et du fort eclatement de leur champ cristallin necessaire a l'elaboration de lasers quasi-3 niveaux.

De plus l'etude fine et systematique des proprietes microscopiques de nouveaux materiaux s'avere toujours tres interessante du point de vue de la recherche fondamentale, c'est ainsi que de nouveaux modeles sont concus par exemple pour le champ cristallin ou que de nouvelles proprietes inhabituelles sont decouvertes, menant a de nouvelles applications.

Ainsi d'autres materiaux dopes a l'ytterbium sont connus pour leurs proprietes de couplage electron-phonon, de couplage magnetique, d'emission cooperative ou encore de bistabilite optique, mais ces proprietes n'ont encore jamais ete mises en evidence dans Yb:Y 2SiO5, Yb:Lu2SiO5 et Yb:Sc2SiO 5.

Nous utilisons principalement les techniques d'absorption IR et de spectroscopie Raman pour determiner les excitations du champ cristallin et les modes de vibration dans le materiau. Eco toxicological effects of 2,4,7,9- tetramethyl decyne-4,7-diol TMDD in zebrafish Danio rerio and permanent fish cell cultures.

The physicochemical properties and slow biodegradation rate of TMDD indicate a low bioaccumulation potential but a high prevalence in the environment. As a consequence, TMDD has been detected in several European rivers in the nanogram per liter and lower microgram per liter range; however, its environmental risk to aquatic organisms is considered low.

Recent studies almost exclusively focused on acute effects by TMDD, little is known about cytotoxic and genotoxic effects, reproduction and developmental toxicity, endocrine disruption, and any kind of long-term toxicity and carcinogenicity so far. The present study aims to provide more specific baseline information on the ecotoxicological effects of TMDD in fish.

For this end, cyto- and genotoxicity assays were carried out in vitro with the permanent fish cell line RTL-W1; in addition, in vivo studies were conducted with the early life stages of zebrafish Danio rerio in order to fill the data gaps in developmental toxicity and endocrine disruption. TMDD showed a cytotoxic and slight genotoxic potential in fish cell lines; moreover, various sublethal and lethal effects could be detected in developing zebrafish embryos.

There was no evidence of endocrine-disrupting effects by TMDD; however, mortality following prolonged exposure to TMDD during fish sexual development test was clearly higher than mortality in the fish embryo test after h exposure. Our results thus confirmed previous findings of laboratory screening tests, suggesting short-term toxic effects of TMDD in the intermediate, and long-term effects in the lower milligram per liter range.

Complete series of chiral paramagnetic molecular conductors based on tetramethyl -bis ethylenedithio -tetrathiafulvalene TM-BEDT-TTF and Chloranilate-bridged heterobimetallic honeycomb layers. Compounds show a molecular packing strongly influenced by the topology of the inorganic layers and behave as molecular semiconductors with room-temperature conductivity values of ca.

The correlation between crystal structure and conducting behavior has been studied by means of tight-binding band structure calculations which support the observed conducting properties. Biomimetic synthesis of raspberry-like hybrid polymer-silica core-shell nanoparticles by templating colloidal particles with hairy polyamine shell. The nanoparticles composed of polystyrene core and poly[2- diethylamino ethyl methacrylate] PDEA hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core-shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination.

Silica deposition was performed by simply stirring a mixture of the polymeric core-shell particles in isopropanol, tetramethyl orthosilicate TMOS and water at 25 degrees C for 2. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA-silica hybrid shell. The resulting hybrid silica core-shell particles were characterized by transmission electron microscopy TEM , thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy.

TEM studies indicated that the hybrid particles have well-defined core-shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA-silica hybrid shell could be well controlled by adjusting the silicification conditions.

These new hybrid core-shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules. Synthesis of 2,2,4,4- tetramethyl -N,N'-bis 2,6-dimethylphenyl cyclobutane-1,3-diimine , a unique compound from Arundo donax, and its analogues to test their antifeedant activity against the boll weevil, Anthonomus grandis. Real-time imaging of nitric oxide production in living cells with 1,3,5,7- tetramethyl -2,6-dicarbethoxy 3',4'-diaminophenyl -difluoroboradiaza-s-indacence by invert fluorescence microscope.

Although the importance of nitric oxide NO as a signalling molecule in many biological processes is becoming increasingly evident, many proposed and potential biological functions of NO still remain unclear. Bioimaging is a good technique to visualize observation of nitric oxide in biological samples. NO production in the cells is successfully captured and imaged with fine temporal and spatial resolution. The results prove that the probe combined with inverted fluorescence microscope can be developed into a sensitive and selective method for further study of NO release from cells.

Development of a new fluorescent probe: 1,3,5,7- tetramethyl 4'-aminophenyl -4,4-difluorobora-3a,4a-diaza- s-indacence for the determination of trace nitrite. A new fluorescent probe, 1,3,5,7- tetramethyl 4'-aminophenyl -4,4-difluorobora-3a,4a-diaza- s-indacence TMABODIPY has been developed for the determination of trace nitrite in terms of the reaction of nitrite with TMABODIPY first in acidic solution and then in alkaline solution to form diazotate, a stable and highly fluorescent reagent.

The method offered the advantage of specificity, sensitivity and simplicity. The proposed method has been applied to monitor the trace nitrite in drinking water and vegetable without extraction. Determination of fatty acids in bio-samples based on the pre-column fluorescence derivatization with 1,3,5,7- tetramethyl butyrethylenediamine-difluoroboradiaza-s-indacene by high performance liquid chromatography.

By using TMBB-EDAN, a sensitive and rapid method based on high performance liquid chromatography-fluorescence detection for the determination of twelve fatty acids FAs in bio-samples has been developed. The proposed method offers advantages of milder derivatization condition and much better sensitivity for the determination of FAs, when compared to the reported fluorescence derivatization-based methods.

In nature, cells perform a variety of complex functions such as sensing, catalysis, and energy conversion which hold great potential for biotechnological device construction. However, cellular sensitivity to ex vivo environments necessitates development of bio—nano interfaces which allow integration of cells into devices and maintain their desired functionality.

Thus, the ability to encapsulate various cell types in either a multi cell S. Matrix molecularly imprinted mesoporous sol-gel sorbent for efficient solid-phase extraction of chloramphenicol from milk. Highly selective and efficient chloramphenicol imprinted sol-gel silica based inorganic polymeric sorbent sol-gel MIP was synthesized via matrix imprinting approach for the extraction of chloramphenicol in milk.

Non-imprinted sol-gel polymer sol-gel NIP was synthesized under identical conditions in absence of template molecules for comparison purpose. Both synthesized materials were characterized by Scanning Electron Microscopy SEM , Fourier Transform Infrared Spectroscopy FT-IR and nitrogen adsorption porosimetry, which unambiguously confirmed their significant structural and morphological differences. The effect of critical extraction parameters flow rate, elution solvent, sample and eluent volume, selectivity coefficient, retention capacity was studied in terms of retention and desorption of chloramphenicol.

Competition and cross reactivity tests have proved that sol-gel MIP sorbent possesses significantly higher specific retention and enrichment capacity for chloramphenicol compared to its non-imprinted analogue. The maximum imprinting factor IF was found as 9.

The sol-gel MIP was found to be adequately selective towards chloramphenicol to provide the necessary minimum required performance limit MRPL of 0. Intra and. Interaction between synthetic analogues of quinoxaline antibiotics and nucleic acids: role of the disulphide cross-bridge and D-amino acid centres in des-N- tetramethyl -triostin A.

They also raise the Tm of poly rA. A Scatchard plot for binding to poly dA-dT determined by solvent partition and spectrophotometric methods shows marked evidence of cooperativity with an intrinsic association constant 1. The consequences of epimerising one of the D-Ser residues appear as disastrous as epimerising both. See DOI: The presented study demonstrates the ability of electrochemistry to employ TMPD to detect bacteria and quantify the activity of bacterial cytochrome c oxidases.

Cyclic voltammetry studies and chronoamperometry measurements performed on the model organism Bacillus subtilis result in a turnover number, calculated for single bacteria. Furthermore, trace amounts of cytochrome c oxidases were revealed in aerobically cultured Escherichia coli, which to our knowledge no other technique is currently able to quantify in molecular biology.

The reported technique could be applied to a variety of pathogenic bacteria and has the potential to be employed in future biosensing technology. Characterization of the activity of L-ascorbic acid 2-[3,4-dihydro-2,5,7,8- tetramethyl 4,8,trimethyltridecyl -2Hbe nzopyranyl-hydrogen phosphate] potassium salt in hydroxyl radical elimination. An environmentally benign route for the development of compressible, thermally insulating and fire retardant aerogels through self-assembling the silk fibroin biopolymer inside the silica structure - An approach towards 3D printing of aerogels.

Thanks to the exceptional materials properties of silica aerogels, this fascinating highly porous material has found high performance and real-life applications in various modern industries. However, a requirement for a broadening of these applications is based on the further improvement of their properties especially with regard to mechanical strength and post-synthesis processability with minimum compromise to the other physical properties.

Here, we report an entirely novel, simple and aqueous based synthesis approach to prepare mechanically robust aerogel hybrids by co-gelation of silk fibroin SF biopolymer, extracted from silkworm cocoons. The synthesis is based on a one-step sequential processes of acid catalysis physical crosslinking of the SF biopolymer and simultaneous polycondensation of tetramethyl orthosilicate TMOS , in the presence of 5- trimethoxysilyl pentanoic acid TMSPA as a coupling agent and subsequent solvent exchange and supercritical drying.

As a further advantage, the formulated hybrid silica-SF aerogel showed an excellent printability in the wet state using a micro-extrusion based 3D printing approach. Microstructure investigation on micropore formation in microporous silica materials prepared via a catalytic sol-gel process by small angle X-ray scattering. The so-called sol-gel technique has been shown to be a template-free, efficient way to create functional porous silica materials having uniform micropores.

This appears to be closely linked with a postulation that the formation of weakly branched polymer-like aggregates in a precursor solution is a key to the uniform micropore generation. However, how such a polymer-like structure can precisely be controlled, and further, how the generated low-fractal dimension solution structure is imprinted on the solid silica materials still remain elusive. Here we present fabrication of microporous silica from tetramethyl orthosilicate TMOS using a recently developed catalytic sol-gel process based on a nonionic hydroxyacetone HA catalyst.

Small angle X-ray scattering SAXS , nitrogen adsorption porosimetry, and transmission electron microscope TEM allowed us to observe the whole structural evolution, ranging from polymer-like aggregates in the precursor solution to agglomeration with heat treatment and microporous morphology of silica powders after drying and hydrolysis. Using the HA catalyst with short chain monohydric alcohols methanol or ethanol in the precursor solution, polymer-like aggregates having microscopic correlation length or mesh-size 2 nm in the solid product due to apertures between the particle-like aggregates.

The data demonstrate that the extremely fine porous silica architecture comes essentially from a gaussian polymer-like nature of the silica aggregates in the precursor having the microscopic mesh-size and. Tocopherol metabolites 2, 5, 7, 8- tetramethyl 2'-carboxyethyl hydroxychroman alpha-CEHC and 2, 7, 8-trimethyl 2'-carboxyethyl hydroxychroman gamma-CEHC in human serum after a single dose of natural vitamin E. To assess over-time changes of serum levels of alpha- and gamma-CEHC in humans after a single dose of vitamin E from a natural source.

Twenty-one healthy subjects ingested a single dose of vitamin E mg of RRR-alpha-tocopherol and 1. Blood was collected before baseline and 2, 6, 12, 24, 35, 50, and 74 h after ingestion. After vitamin E ingestion, a statistically significant increase was observed for alpha-tocopherol and alpha-CEHC.

Maximum serum levels for both compounds were measured 12 h after application While gamma-tocopherol levels decreased during the study period, an increase in the metabolite gamma-CEHC was observed. The appearance of the metabolite in blood parallels that of the parent compound. The gamma-tocopherol analog appears to be metabolized more efficiently than alpha-tocopherol. The paper describes development of a sol-gel based immunoaffinity method for the steroid hormone levonorgestrel LNG and the effects of changes in the sol-gel matrix format on the activity of the entrapped antibodies Abs and on matrix structure.

No activity was obtained with a TMOS :water ratio of , most likely because of the very dense polymer that resulted from these polymerization conditions. Only minor differences in the non-specific binding were obtained with the various formats.

Confocal fluorescent microscopy with fluorescein isothiocyanate FITC labeled immunoglobulines IgGs entrapped in the sol-gel matrix showed that the entrapped Abs were distributed homogenously within the gel. Scanning electron microscopy SEM images have shown the diverse structures of the various sol-gel formats and precursors.

We have studied temperature- and electric-field-dependent carrier transport in single flakes of MoS2 treated with n -butyllithium. The temperature dependence of the four-terminal resistance follows the Efros-Shklovskii variable range hopping conduction mechanism.

From measurements in the Ohmic and non-Ohmic regime, we estimate the localization length and the average hopping length of the carriers, as well as the effective dielectric constant. Furthermore, a comparison between two- and four-probe measurements yields a contact resistance that increases significantly with decreasing temperature. Spectral hole lifetimes and spin population relaxation dynamics in neodymium-doped yttrium orthosilicate.

Cruzeiro, E. Zambrini; Tiranov, A. At the lowest temperature of 3 K we find a general trend where the lifetime is short at low field strengths, then increases to a maximum lifetime at a few hundred mT, and then finally decays rapidly for high field strengths. The maximum lifetime depends strongly on both the field strength and orientation, due to the competition between these processes and their different angular dependencies.

By decreasing the concentration to less than 1 ppm we could completely eliminate the cross relaxation, reaching a lifetime of 3. At higher temperatures the spectral hole lifetime is limited by the magnetic-field-independent Raman and Orbach processes.

In addition we show that the cross relaxation rate can be strongly reduced by creating spectrally large holes of the order of the optical inhomogeneous broadening. Our results are important for the development and design of new rare-earth-ion doped crystals for quantum information processing and narrow-band spectral filtering for biological tissue imaging. Kinetic analysis for cyclic CO2 capture using lithium orthosilicate sorbents derived from different silicon precursors.

The CO2 sorption kinetics predominantly followed the nucleation mode and could be accurately described by the Avrami-Erofeev model. The Avrami-Erofeev model provided an in-depth analysis of correlation between sorption performance and material properties.

Both the nucleation speed and nucleation dimensionality affected the overall sorption kinetics. For the cyclic tests, the precipitated-silica-derived sample presented the poorest performance with the capacity decreasing from However, the sample made from fumed silica displayed an opposite trend with the capacity increasing from The radically distinct behaviour of samples during cycles was on account of the alternation of sorption kinetics.

A reverse microemulsion technique has been used to synthesize quantum dot nanocomposites within a SiO2 surface coating. The resulting monolith was transparent and fluorescent under ultraviolet UV lamp. Moreover the monolith produced was crack-free. Further studies on the photo stability of the monolith were performed using a high power UV LED device.

Remarkably, quantum dots in the SiO, monolith showed better photo stability compared with those dispersed in a polymer matrix. This study evaluated biological treatment of TMAH in a full-scale methanogenic up-flow anaerobic sludge blanket UASB followed by an aerobic bioreactor. The batch test results confirmed that the UASB sludge under methanogenic conditions would be favored over the aerobic ones for TMAH treatment due to its superb ability of handling high strength of TMAH-containing wastewaters.

Tetra-methyl substituted copper II phthalocyanine as a hole injection enhancer in organic light-emitting diodes. We have enhanced hole injection and lifetime in organic light-emitting diodes OLEDs by incorporating the isomeric metal phthalocyanine, CuMePc, as a hole injection enhancer.

The effect of CuMePc thickness on device performance was investigated. Atomic force microscope AFM studies revealed that the thin films were smooth and uniform because the mixture of CuMePc isomers depressed crystallization within the layer. A Pauson-Khand type of conversion of enynes to bicyclic cyclopentenones employing the commercially available Co2 CO 8 and tetramethylthiourea TMTU as catalysts is described. This method allows a variety of enynes with diverse functional groups to be cyclized into cyclopentenones of interest.

Anisotropy and phonon modes from analysis of the dielectric function tensor and the inverse dielectric function tensor of monoclinic yttrium orthosilicate. We determine the frequency dependence of the four independent Cartesian tensor elements of the dielectric function for monoclinic symmetry Y2SiO5 using generalized spectroscopic ellipsometry from cm Three different crystal cuts, each perpendicular to a principle axis, are investigated.

We apply our recently described augmentation of lattice anharmonicity onto the eigendielectric displacement vector summation approach [A. Mock et al. B 95, , We obtain an excellent match between all measured and model-calculated dielectric function tensor elements and all dielectric loss function tensor elements. We obtain 23 Au and 22 Bu symmetry long-wavelength active transverse and longitudinal optical mode parameters including their eigenvector orientation within the monoclinic lattice.

We perform density functional theory calculations and obtain 23 Au symmetry and 22 Bu transverse and longitudinal optical mode parameters and their orientation within the monoclinic lattice. We compare our results from ellipsometry and density functional theory and find excellent agreement.

We also determine the static and above reststrahlen spectral range dielectric tensor values and find a recently derived generalization of the Lyddane-Sachs-Teller relation for polar phonons in monoclinic symmetry materials satisfied [M. Schubert, Phys Rev.

Dual color emitting Eu doped strontium orthosilicate phosphors synthesized by bio-template assisted ultrasound for solid state lightning and display applications. It was evident that the morphological growth was highly reliant on A. The formation mechanisms for different hierarchical SS were proposed. The concentration quenching phenomenon was discussed which attributes to energy transfer, electron-phonon coupling and ion-ion interaction.

The Judd-Ofelt intensity parameters and other radiative properties were estimated by using emission spectra. Luminescence decay and quantum yield suggest the suitability of this phosphor as an efficient luminescent medium for light emitting diodes. Effects of tetraethyl orthosilicate TEOS on the light and temperature stability of a pigment from Beta vulgaris and its potential food industry applications.

A novel, simple and inexpensive modification method using TEOS to increase the UV light, pH and temperature stability of a red-beet-pigment extracted from Beta vulgaris has been proposed. The effects on the molecular structure of betalains were studied by FTIR spectroscopy.

The presence of betacyanin was verified by UV-Vis spectroscopy and its degradation in modified red-beet-pigment was evaluated and compared to the unmodified red-beet-pigment; performance improvements of Polar diagrams of color by unmodified and modified red-beet-pigment in models of a beverage and of a yogurt were obtained and the color is preserved, although here is a small loss in the chromaticity parameter of the modified red-beet-pigment.

Mesoporous titanosilicates with high loading of titanium synthesized in mild acidic buffer solution. The mixture of sodium silicate and EGMS was proved to be the best silicon source for the synthesis of titanosilicates with ordered mesostructure and high titanium content. The efficiency of this synthetic method may be attributed to the mild acidic medium as well as the modified hydrolysis-condensation rate and hydrophility of the precursors.

Explosion and combustion properties of alkylsilanes I : temperature-composition limits of explosion for methyl-,dimethyl-,trimethyl-, tetramethyl -,and vinylsilane at atmospheric pressure. The explosion limits of five alkylsilanes were determined as a function of temperature and composition at a pressure of 1 atmosphere. Explosion limits for hydrocarbons analogous to these silanes fall in a temperature range of degrees to degrees C.

Since the explosion temperatures of the alkylsilanes are lower than those of the hydrocarbons and since they decrease as hydrogen atoms are substituted for methyl groups, it was concluded that the Si-H bond is more readily susceptible to oxidation than the C-H bond. This study evaluated TMAH biodegradation under methanogenic conditions. Furthermore, several chemicals including some surfactants, DMSO, and sulfate were examined for their potential inhibitory effects on TMAH biodegradation under methanogenic conditions.

Increase in the electron-withdrawing character of the substituent at these positions leads to an upfield shift of the signal for the nitrone carbon atom, and this corresponds to the increase in electron density on it.

The mol-ecule of the title compound, C 18 H 28 N 2 , composed of two 2,5-dimethyl-pyrrole groups linked by a hexane chain, lies across a crystallographic inversion centre. The mean plane of the pyrrole ring is almost perpendicular to the mean plane of the central chain, making a dihedral angle of Month, Day Effect of tone mapping operators on visual attention deployment. From an artistic intention point of view, TMOs are not necessarily transparent and might induce different behavior to view the content.

To that end both objective and subjective tests in the form of eye-tracking experiments have been conducted on several still image content that have been processed by 11 different TMOs. Our studies confirm that TMOs can indeed modify human attention and fixation behavior significantly. Since the existing studies so far have only considered the quality or aesthetic appeal angle, this study brings in a new perspective regarding the importance of VA in HDR content processing for visualization on LDR displays.

The pyran ring adopts a boat conformation whereas the two fused cyclo-hexane rings adopt envelope conformations in both mol-ecules. Anomelies are considered to be minor varients from the normal, such as In the title compound, C 23 H 25 NO 5 , the pyran ring adopts a flattened boat conformation, while the two cyclo-hexenone rings are in envelope conformations.

The 3-nitro-phenyl ring is almost perpendicular to the pyran ring, making a dihedral angle of Conformational polymorphism and thermochemical analysis of 5,5' ''-bis[ 2,2,5,5- tetramethyl aza-2,5-disilacyclopentyl ethyl]-2,2':5',2' ':5' ',2' ''-quaterthiophene.

The titled compound exists as two polymorphic solid phases denoted form-I and form-II. Form-I obtained by as-synthesized material is a more stable phase. Form-II is a less stable phase. The solid-solute-solid transformation recrystallization from solution from form-II to form-I is also observed. In contrast, form-II is obtained only by a solid-melt-solid transformation from form-I.

Therefore, the system of two polymorphs is monotropic. The solid-state NMR measurement shows that form-I has the molecular conformation of complete S-syn-anti-syn in the oligothiophene backbone, whereas form-II has that of S-all-anti. With the solution NMR data, the polymorphism could not be observed.

Therefore, the polymorphs originate from the different molecular packing involving the conformational change of the molecule. This unique property is attributed to the extra bulky terminal groups of the compounds. However, despite the extra bulky terminal groups, the mentioned polymorphism is not observed in the titled compound analogue which has S-all-anti conformation like form-II. Use of sol-gels as solid matrixes for simultaneous multielement determination by radio frequency glow discharge optical emission spectrometry: determinations of suspended particulate matter.

A new approach for the analysis of particulate matter by radio frequency glow discharge optical emission spectrometry rf-GD-OES is described. Dispersion of the particles in a sol-gel sample matrix provides a convenient means of generating a thin film suitable for sputter-sampling into the discharge.

Acid-catalyzed sol-gel glasses synthesized from tetramethyl orthosilicate were prepared and spun-cast on glass substrates. The resultant thin films on glass substrates were analyzed to determine the discharge operating conditions and resultant sputtering characteristics while a number of optical emission lines of the film components were monitored. Use of the sol-gels as sample matrixes allows for background subtraction through the use of analytical blanks and may facilitate the generation of calibration curves via readily synthesized, matrix-matched analytical standards in solids analysis.

This preliminary study demonstrates the possibility of incorporating various insoluble species, including ceramics and geological specimens in powder form, into a solid matrix for further analysis by either rf-GD-OES or MS. The black citrus aphid, also known as the tea aphid, Toxoptera aurantii Boyer attacks economically important crops, including tea Camellia sinensis L. In the current study, silica sol-gel formulations were screened to find one that could carry and release C.

The common plant volatile transhexenal was used as a model molecule to screen for suitable sol-gel formulations. A sol-gel formulation containing tetramethyl orthosilicate and methyltrimethoxysilane in an vol:vol ratio was selected to develop a slow-release dispenser. The half-life of transhexenal in the sol-gel dispenser increased slightly with the volume of this compound in the dispenser. Ten different volatiles were tested in the sol-gel dispenser.

Alcohols of carbons had the longest half-lives 3. Release of these volatiles from the dispensers could not be detected by the zNose after 16 d cishexenyl acetate to 26 d 3,7-dimethylocta-1,6-dienol. The sol-gel dispensers performed adequately for the slow release of plant volatiles to trap aphids in the greenhouse. Rooftop solar thermal collectors have the potential to meet residential heating demands if deployed efficiently at low solar irradiance i.

The efficiency of solar thermal collectors depends on their ability to absorb incoming solar energy and minimize thermal losses. Most techniques utilize a vacuum gap between the solar absorber and the surroundings to eliminate conduction and convection losses, in combination with surface coatings to minimize reradiation losses. Here, we present an alternative approach that operates at atmospheric pressure with simple, black, absorbing surfaces.

Silica based aerogels coated on black surfaces have the potential to act as simple and inexpensive solar thermal collectors because of their high transmission to solar radiation and low transmission to thermal radiation. To demonstrate their heat-trapping properties, we fabricated tetramethyl orthosilicate -based silica aerogels.

To provide a deeper understanding of the link between aerogel properties and overall efficiency, we developed a coupled radiative-conductive heat transfer model and used it to predict solar thermal performance. This study sheds light on the applicability of silica aerogels on black coatings for solar thermal collectors and offers design priorities for next-generation solar thermal aerogels.

Engineering magnetism at functional oxides interfaces: manganites and beyond. The family of transition metal oxides TMOs is a large class of magnetic materials that has been intensively studied due to the rich physics involved as well as the promising potential applications in next generation electronic devices.

In TMOs , the spin, charge, orbital and lattice are strongly coupled, and significant advances have been achieved to engineer the magnetism by different routes that manipulate these degrees of freedom. The family of manganites is a model system of strongly correlated magnetic TMOs. In this review, using manganites thin films and the heterostructures in conjunction with other TMOs as model systems, we review the recent progress of engineering magnetism in TMOs.

We first discuss the role of the lattice that includes the epitaxial strain and the interface structural coupling. Then we look into the role of charge, focusing on the interface charge modulation. Having demonstrated the static effects, we continue to review the research on dynamical control of magnetism by electric field. Next, we review recent advances in heterostructures comprised of high T c cuprate superconductors and manganites.

Following that, we discuss the emergent magnetic phenomena at interfaces between 3d TMOs and 5d TMOs with strong spin-orbit coupling. Finally, we provide our outlook for prospective future directions. Low-temperature solution-processed hydrogen molybdenum and vanadium bronzes for an efficient hole-transport layer in organic electronics. A simple one-step method is reported to synthesize low-temperature solution-processed transition metal oxides TMOs of molybdenum oxide and vanadium oxide with oxygen vacancies for a good hole-transport layer HTL.

The oxygen vacancy plays an essential role for TMOs when they are employed as HTLs: TMO films with excess oxygen are highly undesirable for their application in organic electronics. Photodynamic therapy PDT has garnered immense attention as a minimally invasive clinical treatment modality for malignant cancers. However, its low penetration depth and photodamage of living tissues by UV and visible light, which activate a photosensitizer, limit the application of PDT.

Densification of porous refractory substrates. A hydrolyzed tetraethyl orthosilicate is applied to the surface of a porous refractory substrate following which the substrate is heated to a temperature and for a period of time sufficient to bond the silica released from the tetraethyl orthosilicate to the substrate. The surface is thus densified and strengthened. Kinetically designed conditions for the catalytic formation of disfavored products.

Various kinetic tests have been applied to show that this is the result of a sequence of two electron transfer steps. Dattelbaum, Andrew M. Fluorescent composites of surfactant-wrapped single-walled carbon nanotubes SWNTs were prepared by exposing suspensions of surfactant-wrapped carbon nanotubes to tetramethylorthosilicate TMOS vapor. Fluorescent aerogels were prepared by replacing water in the gels with methanol and then exposing them to supercritical fluid drying conditions.

The aerogels can be used for gas sensing. At 72 h after reperfusion, all animals' neurologic deficit scores were evaluated. Cerebrums were removed and cerebral infarction volume was measured. The expression of thioredoxin and thioredoxin reductase mRNA was determined at 6 and 24 h after reperfusion.

Cerebral infarction volume and neurological deficit scores were significantly decreased in the group with tetramethyl pyrazine treatment. Treatment with tetramethyl pyrazine, within 4 h after reperfusion, protects the brain from ischemic reperfusion injury in rats.

The neuroprotective mechanism of tetramethyl pyrazine treatment is, in part, mediated through the upregulation of thioredoxin transcription. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. With rapid research progress in this field, a timely account of this advanced technology is highly necessary.

Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed. Hole polaron-polaron interaction in transition metal oxides and its limit to p-type doping. Traditionally the origin of the poor p-type conductivity in some transition metal oxides TMOs was attributed to the limited hole concentration: the charge-compensating donor defects, such as oxygen vacancies and cation interstitials, can form spontaneously as the Fermi energy shifts down to near the valence band maximum.

Besides the thermodynamic limit to the hole concentration, the limit to the hole mobility can be another possible reason, e. Although isolated hole polarons had been found in some TMOs , the polaron-polaron interaction is not well-studied. Here we show that in TMOs such as TiO2 and V2O5, the hole polarons prefer to bind with each other to form bipolarons, which are more stable than free hole carriers or separated polarons.

This pushes the hole states upward into the conduction band and traps the holes. The rise of the Fermi energy suppresses the spontaneous formation of the charge-compensating donor defects, so the conventional mechanism becomes ineffective. Since it can happen in the impurity-free TMO lattices, independent of any extrinsic dopant, it acts as an intrinsic and general limit to the p-type conductivity in these TMOs.

An open architecture motion controller. Nomad, an open architecture motion controller, is described. Nomad software runs in a UNIX environment and provides for sensor-controlled robotic motions, with user replaceable kinematics. It can also be tailored for highly specialized applications.

Open controllers such as Nomad should have a major impact on the robotics industry. Lithium-ion batteries LIBs have been widely used in the field of portable electric devices because of their high energy density and long cycling life.

Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li-ion during the reaction, and accommodate volume expansion during cycling. Objective quality assessment of tone-mapped images. Different TMOs create different tone-mapped images, and a natural question is which one has the best quality. Without an appropriate quality measure, different TMOs cannot be compared, and further improvement is directionless.

Subjective rating may be a reliable evaluation method, but it is expensive and time consuming, and more importantly, is difficult to be embedded into optimization frameworks. Here we propose an objective quality assessment algorithm for tone-mapped images by combining: 1 a multiscale signal fidelity measure on the basis of a modified structural similarity index and 2 a naturalness measure on the basis of intensity statistics of natural images.

Validations using independent subject-rated image databases show good correlations between subjective ranking score and the proposed tone-mapped image quality index TMQI. Furthermore, we demonstrate the extended applications of TMQI using two examples-parameter tuning for TMOs and adaptive fusion of multiple tone-mapped images.

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In order to ensure "consistent and proportional" punishments for offenders, ESIC came up with a "Sanctions Matrix" that breaks down like this:. The list includes amended sanctions against two of the players who were suspended for a year in October: Akram "adk" Smida previously playing as "akram" has had his suspension extended to two years, while Daryl "mayker" May will now sit for four years.

The commission specified that the suspensions arise strictly from betting on matches in ESIC member events and do not address potential allegations of match fixing, although it added that "the strong possibility of this in a number of cases is still under investigation by both ESIC and law enforcement. It also stated that it detected "collusive behavior by close associates" of the suspended players, specifically that there were several instances where they placed bets identical to those placed by the players themselves.

Because these people are not CS:GO players, they do not fall within ESIC's jurisdiction, and so it has "referred their behaviour to law enforcement for investigation as being potentially in breach of criminal law" instead. However, ESIC is of the view that there is a high possibility that it will issue match-fixing charges arising from the ongoing investigations, potentially including against players sanctioned today.

It's a big, sweeping ban, and the threat of law enforcement involvement is no doubt unnerving for those involved, especially since the amounts of money involved were likely not all that great. These are not top-tier pros battling it out at The Majors, after all. But the announcement also includes a reminder of ESIC's rules against betting on matches, and more pointedly, why it pursues offenders so vigorously:.

Without a unified understanding of the implications of inappropriate betting behaviour and observance of anti-corruption mechanisms such as the Anti-Corruption Code , esports runs the risk of facilitating attractive fraud opportunities for bad actors. WTFSkins offers exciting games to its users, and you have access to an attractive signup bonus coupled with several daily bonuses. A little set back of the WTFSkins is the customer support, it takes a while before you receive a response, but you definitely would!

If you want to receive free bonus skins on the site, make sure you get started by registering and making your first deposit. The are as follows:. Due to its nature, there are a few questions that require clarification. CSGO is an online game launched in , and this game mainly pits players against themselves online.

It was last updated a couple of months ago, and this update has introduced a new build of CS: GO. It has several distinct game modes like bomb prevention, deathmatches, defuse the bomb, etc. A roulette coinflip is one of the most thrilling game types you can find on CSGO. A coinflip consists of two main players without the interference of a third party.

The CSGO site produces a coin side, any player that picks the same side gets all the wagered skins. Case unboxing is popular and is definitely on our list of best CSGO games. There are Case opening CSGO betting sites that allow you to deposit either real money or skins in exchange for credits. This also gives clear access to choose and open a premade case or a personally designed one. Jackpot is an esports betting game where you play against many players. The idea of the game is for all players to bet their skins into a pot.

Your win percentage is hinged on the worth of the skin you wagered. The site will eventually pick a winner after calculating the user with the highest value of skins. The truth is, the more you wager, the higher your chances of winning. CSGO roulette is not a far cry from regular roulette, one of the popular casino games. It has three-wheels blue, yellow, and green. On most gambling websites, black and yellow reels have an x2 multiplier, while the green multiplier is x While the number of CSGO betting sites keeps surging, the need to identify the legit sites has become even more important.

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